Here we report a series of dimeric phosphinodiboranate complexes with trivalent f‐metals that show how shorter‐than‐expected U−B distances indicative of increased covalency give rise to measurable differences in solution deoligomerization reactivity when compared to isostructural complexes with similarly sized lanthanides. These results, which are in excellent agreement with supporting DFT and QTAIM calculations, afford rare experimental evidence concerning the measured effect of variations in metal‐ligand covalency on the reactivity of trivalent uranium and lanthanide complexes.Qualitative differences in the reactivity of trivalent lanthanide and actinide complexes have long been attributed to differences in covalent metal‐ligand bonding, but there are few examples where thermodynamic aspects of this relationship have been quantified, especially with U Here we report experimental and computational studies that quantify the measured effect of variations in metal‐ligand covalency on the reactivity of phosphinodiboranate complexes with trivalent uranium and similarly sized lanthanides. Moreover, Shafer, Yang, and co‐workers attributed the ca. 1 kcal mol−1 free energy differences for stepwise binding of picolinate ligands to heavy trivalent actinides to energy degeneracy driven covalency.One of the most critical debates in f‐element science continues to center on the role of covalent metal‐ligand bonding on the reactivity of trivalent lanthanide and actinide complexes. It has been shown, for example, how competing variables  could account for some empirical differences in reactivity.While the existence of covalency in certain trivalent actinide‐ligand bonds is settled,3+ are unstable with respect to oxidation in air and water.As illustrated in the examples above, aqueous reactivity comparisons with trivalent actinides are typically limited to transplutonium elements because early actinides like U3BNMe2BH3−) can give rise to covalency‐induced differences in reactivity. Pr(H3BNMe2BH3)3 and U(H3BNMe2BH3)3, for example, are isostructural coordination polymers in the solid state, but Pr(H3BNMe2BH3)3 readily depolymerizes and sublimes when heated under vacuum whereas U(H3BNMe2BH3)3 does not (Scheme 3BNMe2BH3)3 and Ln(H3BNMe2BH3)3 complexes can be attributed to increased covalent U−H−B bonding in bridging DMADB ligands that prevents depolymerization required for U(H3BNMe2BH3)3 to sublime.In this context, it has been proposed that trivalent lanthanide and uranium complexes containing borohydride ligands such as DMADB (Ht Scheme a.[14] tBu‐PDB) can also be used to prepare homoleptic complexes with trivalent lanthanides and uranium (Scheme 2(H3BPtBu2BH3)6 with M=U, Nd, and Er showed that these complexes exist as dimers in the solid‐state regardless of the metal size but depolymerize to different extents when dissolved in aromatic solvents such as benzene. Our initial studies of M2(H3BPtBu2BH3)6 complexes revealed that they are difficult to prepare using conventional solution‐based salt elimination reactions, which impeded subsequent efforts to investigate their bonding and thermochemical properties thoroughly. Recently, we overcame this obstacle and showed that M2(H3BPtBu2BH3)6 and related phosphinodiboranate complexes can be prepared more reproducibly in higher yields using mechanochemical methods.Phosphorus congeners of aminodiboranates like DMADB called ditertbutylphosphinodiboranates 6 with a complete series of lanthanides  and U3+ that allowed us to quantify the extent to which the identity of the metal ion influences the energy of deoligomerization in solution. The experimental results, which are corroborated by supporting density functional theory (DFT) calculations, quantify small but significant differences between the lanthanides and U3+ in their covalent metal‐ligand bonding, correlating to measurable differences in their solution reactivity.Here, then, we report the mechanochemical synthesis and structures of MtBu‐PDB complexes were prepared by grinding three equivalents of K(H3BPtBu2BH3) with one equivalent of LnI3 (Ln=La–Nd), SmBr3, or UI3(thf)4 using stainless steel balls. The complexes were isolated by extracting the ground solid‐state mixture with Et2O or chlorobenzene and subsequently crystallized from pentane mixtures.2(H3BPtBu2BH3)6, which gave consistently lower yields (<10 %). It is not clear why the yield was lower with La, but similar results have been reported for the synthesis of La(H3BNMe2BH3)3(thf) from LaCl3, as compared to the same reaction with other lanthanide chlorides.The tBu‐PDB complexes revealed that they exist as dimers in the solid state like U2(H3BPtBu2BH3)6 and Nd2(H3BPtBu2BH3)6.tBu‐PDB ligands that hold the dimeric structure together. The M−B distances for the chelating tBu‐PDB ligands are on average ca. 0.2 Å longer than those for the bridging ligands, and they suggest that the denticity of the associated BH3 groups are κ2 and κ3, respectively.Single‐crystal XRD studies of the new 2(H3BPtBu2BH3)6 complexes, we plotted the M−B bond lengths as a function of the ionic radii of the trivalent metal.3+ with R2=0.98. In contrast, the plot of the average bridging M−B distances vs. ionic radii shows that the bridging U−B distances are ca. 0.04 Å shorter than their expected position based on the line fit to the Ln−B distances (R2=0.98). The shorter than expected bridging U−B distances suggest that the U−H−B bonds are more covalent than the Ln−H−B bonds. Consistent with this analysis, we have shown that bond length differences as small as 0.04 Å can give rise to measurable differences in metal‐ligand covalency using ligand K‐edge XAS.2)2]3 complexes.To evaluate the possibility of covalent bonding in M2H3BPtBu2BH362(H3BPtBu2BH3)6 dimers to convert to monomers, we suspected that the thermochemical values associated with this process should reflect the enhanced covalency in the U−H−B bonds. Variable‐temperature 1H NMR studies were therefore carried out on triplicate samples of the complexes with the largest lanthanides (La−Nd) and uranium in C6D6 to quantify changes in the monomer/dimer concentrations as a function of temperature  to 9.4±0.6 kcal mol−1 with La (1.032 Å).−1 shows a significant departure from the predicted value of 9.2 kcal mol−1 based on its ionic radii (1.025 Å) and the linear regression of the lanthanide data points. The increased enthalpy for U indicates that it takes more energy to break up the dimer compared to the lanthanide complexes, which is consistent with the increased metal‐ligand covalency in the bridging ligands.Plotting the ΔH values obtained from the Van't Hoff plots against the ionic radii of the metals reveals a clear distinction between the U and the lanthanide s Figure . The ΔH −1. The difference in ΔG is larger for M=U compared to M=Ce  and M=La , but the values are just outside the experimental uncertainties.As shown in Table 5H4R)3 and Ce(C5H4R)3 (where R=tBu or SiMe3) and various azines (like pyridine) that revealed more exothermic binding to U3+ than Ce3+ that corresponded to shorter U−N distances compared to Ce−N.−1 (8 kJ mol−1) increase in binding enthalpy. Despite the significant difference in ligands, these values are remarkably consistent with the values reported here for the M2(H3BPtBu2BH3)6 complexes with M=U and Ce; the enthalpy difference of 1.6 kcal mol−1 (6.7 kJ mol−1) corresponds to a M−B difference of 0.022 Å.We can compare these results to one of the few reports that has quantified the relationship between metal‐ligand bond length and binding enthalpy in trivalent uranium and lanthanide complexes. Ephritikhine, Berthet, and co‐workers reported NMR experiments with U(C2(H3BPtBu2BH3)6→2 M(H3BPtBu2BH3)3 were also in excellent agreement with experimental values (Table −1) is for the U complex corroborating that deoligomerization requires more energy here than for the lanthanides.For comparison to the experimental results, DFT calculationses Table . The hig2(ρ)), energy density (E(r)), the ratio of potential energy and Lagrangian kinetic energy (|V(r)|/G(r)), and the so‐called bond degree (BD), which is the ratio E(r)/ρ, at the bond critical points are provided in the Supporting Information.To further probe the differences in bonding in the M−B interactions, QTAIM analysis was performed for the U and Ln species. Computed values for the electron density (ρ), Laplacian electron density 6 correlate to small, but significant increases in the enthalpy and Gibbs free energy required to transform the dimer into monomeric units, as compared to identical complexes with larger and smaller lanthanide ions. Specifically, a 0.04 Å decrease in U−B distance corresponds to a 1.3 kcal mol−1 (5.4 kJ mol−1) increase in deoligomerization enthalpy based on linear regressions and comparison of ionic radii.In summary, we have described a series of trivalent f‐metal phosphinodiboranate complexes that allowed the relationship between covalent metal‐ligand bonding and its associated influence on solution reactivity to be quantified. The shorter‐than‐expected bridging U−B distances in U2(H3BPtBu2BH3)6 complexes were conducted on pure complexes in a single non‐polar solvent, the results suggest that differences in deoligomerization enthalpy can be ascribed solely to differences in metal‐ligand covalency. This finding is in excellent agreement with our supporting calculations and appears to provide unambiguous evidence of the quantified influence that metal‐ligand covalency can have on the differing reactivity of trivalent uranium and lanthanides.Because the solution studies with MThe authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re‐organized for online delivery, but are not copy‐edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.Supporting InformationClick here for additional data file.


The activity tests were carried out at a temperature of 750 °C. The research showed that the catalyst prepared from the precursor containing chloride exhibited very low conversions of methane and carbon dioxide. The poisoned catalyst system before and after the calcination process was subjected to Temperature Programmed Surface Reaction tests to determine whether the thermal treatment causes a decrease in the amount of chlorine in the system. To determine the decomposition temperature of the LaCl3 precursor and the nickel chloride NiCl2 compound, the samples were analyzed by Thermogravimetry. Finally, the catalytic samples were tested by Time-of-Flight Secondary Ion Mass Spectrometry analysis to confirm the presence of nickel–chlorine bonds on the surface of the catalytic system.This work investigated the influence of the catalytic support precursor on the activity of nickel catalysts 20%Ni/5%La The order of catalytic activity of metal catalysts supported on Al Ni > Pt . The abs Ni > Pt ,5. For teactions ,18,19,20ormation ,19,20,21ormation . It shou2O3 support [This article investigates the possibility of poisoning the catalyst with chlorine incorporated from the catalytic support precursor. Chlorine may have the effect of reducing or increasing the activity of catalytic systems depending on the process and the type of active phase . Chlorin support , which m3 or La(NO3)3) on the activity of nickel catalysts in the mixed methane reforming process was investigated [In this work, the influence of the support precursor  nitrate, and on the other hand, it was lanthanum (III) chloride. The conducted studies of catalytic activity show that the catalyst with the nitrate precursor showed higher conversions of methane (71%) and carbon dioxide (68%) while the catalyst obtained using chloride precursor was less active. This is due to the formation of bonds between atomic chlorine and metallic nickel, which consequently leads to a smaller number of active sites on the catalytic surface. This phenomenon will be discussed in later sections of the work.In this work, activity tests were carried out in the mixed methane reforming process to compare the influence of the catalytic support precursor on the activity. 3 precursor, temperature-programmed surface reaction tests were performed. The reactions were carried out for the 5%La2O3–95%Al2O3 supports and 20%Ni/5%La2O3–95%Al2O3 catalysts before and after the calcination process. These samples were annealed in a helium atmosphere in the temperature range of 25–900 °C, and the products of the process were recorded with a mass spectrometer. 2O3–Al2O3 catalyst support before and after calcination marked with red and black curves, respectively. The test performed on the support before the calcination process showed that the chlorine was removed from the surface in two steps. The first low-temperature effect is visible in the temperature range of 40–320 °C, while the second high-temperature effect begins at temperatures above about 730 °C. In the case of the calcined support, two combined peaks related to the evolution of hydrogen chloride in the temperature range from 80 to over 900 °C were observed. Comparing both TPSR profiles, it can be stated that the calcination process did not affect the complete removal of chlorine from the sample. It can be assumed that during the calcination process chlorine is removed from the surface of the support, and the remaining chlorine bound in the mass of the sample may be released from it and re-poison the surface, which is confirmed by the performed tests.In order to verify the presence of chlorine in the catalytic systems prepared using the LaClThe next TPSR results for the release of hydrogen chloride for the monometallic nickel catalyst before and after the calcination process are shown in 3 precursor. The TG–DTA studies were carried out to verify the temperature at which lanthanum (III) chloride completely decomposes to the target lanthanum (III) oxide. 3 sample in an air atmosphere. The results of the TG–DTA measurements of LaCl3 showed that the weight loss of the sample included three stages. The TG curve shows rapid weight losses of 34% corresponding to each endothermic peak at 150 °C and 210 °C, respectively in the DTA curve. This weight loss is associated with the dehydration of the sample. The second stage (340–620 °C) is probably connected to the transformation of LaCl3 to LaOCl [2O3, which is accompanied by the endothermic effect at 740 °C. The tests carried out with the thermogravimetric method show that the LaOCl compound is still present at the reaction temperature of 750 °C. This temperature is too low for the complete decomposition of this compound, so the catalytic system may contain chlorine.Chlorine in the form of hydrogen chloride recorded with the mass spectrometer originates from the decomposition of the LaClto LaOCl . The las3 can combine with other components included in the structure of the catalytic system 20%Ni/5%La2O3–95%Al2O3. One of the elements that can form a bond with chlorine is nickel. These elements can create various combinations, but in this work, nickel (II) chloride was subjected to TG–DTA tests. 2 structure. Another effect of the decomposition of the sample is visible in the temperature range of 400–900 °C. This wide mass loss is related to the processes of dehydrochlorination, dichlorination, partial oxidation [Chlorine formed as a result of the decomposition of LaClxidation , and the3 × 7H2O and (ii) NiCl2 × 6H2O of the analysis are presented below.The decomposition reactions of (i) LaCl(i)3 × 7H2O => LaCl3 + 7H2O(a) LaCl3 + O2 => 2LaOCl + 2Cl2(b) 2LaCl3 × 7H2O decomposition  2LaOCl + 0.5O3 × 7H2O sample showed a 4% weight loss (50 mg × 4% = 2 mg). The sample after the second stage had a mass of 24.5 mg (50 mg − 50 mg × 51% weight loss = 24.5 mg of solid residue). The theoretical weight loss was 18% and the experiment showed a value of 8%. The results obtained from the TG tests show that the last stage was not completed due to the too-low temperature (1000 °C), which means that the sample still contains chloride forms in the sample mass.The final decomposition step of the LaCl(ii)2 × 6H2O => NiCl2 + 6H2O NiCl2 × H2O.Due to the fact that the nickel chloride was dried before the measurements, the water content changed. In 2 × H2O => NiCl2 + H2O (b) NiCl2 + O2 => 2NiO +2Cl2(c) 2NiClThe theoretical weight loss in the decomposition of nickel (II) chloride obtained from the calculations was about 49%. However, the conducted thermogravimetric analysis allowed us to estimate the weight loss at the level of 43%. The difference is not too big, but it can be concluded that up to the temperature of 1000 °C nickel (II) chloride does not completely decompose, which means that chlorine can be present both in the mass and on the surface of the discussed catalytic systems.3 and NiCl2 showed that both compounds decompose at high temperatures. This means that the calcined and reduced catalysts still contain some surface and bulk chlorine. The calcination temperature (600 °C) of the La2O3–Al2O3 support does not cause lanthanum (III) chloride to decompose completely, which is confirmed by TG–DTA analysis. Lanthanum (III) chloride decomposition products (chloride forms) can move to other components of the catalyst, e.g., aluminum or nickel, and can bond with them, which could be synonymous with poisoning the catalyst.Analysis of the decomposition of LaCl2O3–95%Al2O3 catalyst reduced at 750 °C is shown in 2O3–95%Al2O3 catalyst after reduction and calcination. Moreover, intensities of the peaks of NiCl2- ions for the system after the calcination process are much lower than that observed for this catalyst after reduction, which implies that the nickel compounds containing chlorine are effectively formed during the reduction in the catalyst.The research results presented above prompted us to use the TOF SIMS technique to investigate the effect of the reduction process on the removal of chlorine from the surface of the catalyst prepared with the use of lanthanum (III) chloride. The TOF-SIMS spectrum of the 20%Ni/5%La3)3 solution (C = 0.5 mol × dm−3). The precipitation process was carried out at the temperature of 80 °C by adding ammonia (as a precipitating agent) to the nitrate solution until the pH of the solution reached values between 9 and 10. The obtained Al(OH)3 was aged for 24 h then filtered and washed using deionized water. In the next step, the obtained precipitate was dried at 100 °C for 1 h and calcined in an air atmosphere for 4 h at 500 °C.Alumina oxide was prepared by precipitation method using an aqueous Al(NO2O3–Al2O3 support was obtained using lanthanum (III) nitrate (C = 0.5 mol × dm−3) and lanthanum(III) chloride (C = 0.5 mol × dm−3). The aqueous nitrate or chloride solutions was added to the previously obtained alumina support. The resulting solutions were left for 24 h followed by evaporation of the solvent. Next, the obtained powder was dried at 100 °C for 1 h, and calcined in air at 600 °C for 4 h. The nominal loading of La2O3 was 5%.La2O3–Al2O3 support surface using a nickel (II) nitrate (C = 0.5 mol × dm−3) precursor. The impregnation process took 12 h. The catalytic material was left for 24 h for impregnation. After the solvent was evaporated, the obtained catalyst was dried at 100 °C and then calcined at 500 °C. The nominal metal content in the obtained catalyst was 20%.The monometallic Ni catalysts were prepared by the wet impregnation method. The nickel was introduced on the obtained Laα radiation source (λ = 1.5418 Å). Data were collected in the 2θ range of 5°–80° with a step size of 0.0167° and exposure per step of 27 s. The conducted XRD tests showed the presence of nickel (II) oxide in the catalyst sample after calcination, while the sample after reduction showed the presence of metallic nickel. No other effects were observed in the diffraction pattern. The formed La2O3 may be non-crystalline and therefore invisible in XRD studies, or its amount may be too small to be visible in the diffraction pattern.The phase transformation of the prepared mixture as a function of temperature was investigated by X-ray diffraction analysis. The diffraction patterns were collected using a PANalytical X’Pert Pro MPD diffractometer in Bragg Brentano reflection geometry . The diffractometer was equipped with a CuK3 and NiCl2 in an air atmosphere. The TG-DTA measurements were carried out using a sample with a weight of 20 mg in a temperature range from 25 to 1000 °C at a linear heating rate of 10 °C/min.TG-DTA analysis, performed on derivatograph MOM 34-27T , was used for the temperature decomposition of the LaCl3+ ions at a 10 kHz repetition rate and an average ion current of 0.4 pA. The analysis time was 30 s for both negative and positive secondary ions giving an ion dose below the static limit of 1 × 1013 ions cm−2.The secondary ion mass spectra were recorded using a TOF-SIMS IV mass spectrometer  equipped with a 25 keV Bi liquid metal primary ion gun and a high mass resolution time of flight mass analyzer. The secondary ion mass spectra were recorded from an approximately 100 μm × 100 μm area of the surface. During measurement, the analyzed area was irradiated with pulses of 25 keV Bi3/min. The evolution of the gaseous products was analyzed as a function of temperature using a mass spectrometer.The temperature-programmed surface reactions (TPSRs) were performed to detect chlorides on the catalytic surface. TPSR measurements were carried out in a quartz reactor using 0.2 g of catalyst in the temperature range of 25–900 °C with a heating rate of 10 °C/min in a helium atmosphere with a volumetric flow of 30 cm4:CO2:H2:H2O:Ar = 2:2:1:0.9:1.25. The total flow of the reaction mixture was 100 cm3/min. In each test, about 0.4 g of catalyst was placed in the reactor. The catalytic activity was measured after the system was stabilized for 3 h. The gas composition before and after the reaction was measured using gas chromatography with thermal conductivity detectors and two chromatographic columns: (I) Molecular Sieve 5A column  and (II) Shin Carbon ST packed column .Tests of catalytic activity in the mixed methane reforming reaction were carried out in a flow-type quartz microreactor under atmospheric pressure at 750 °C. The volume ratio of the reaction reagents in each test was as follows: CHiCH4, WiCO2, and WiAr correspond to the average content of CH4, CO2, or Ar from three surface measurements originating from the injection of the reaction mixture at a given temperature, and W0CH4, W0CO2, and W0Ar correspond to the average of the CH4, CO2, or Ar standard from three surface measurements originating from the injection of the standard mixture.Methane and carbon dioxide conversions ,29 were 2O3–95%Al2O3 catalytic support, chlorine was introduced from the LaCl3 precursor (1). Then, the obtained material was calcined in the air atmosphere at a temperature of 600 °C, which according to TG–DTA tests, did not result in the complete decomposition of lanthanum (III) chloride. Due to this process, compound such as LaClO was obtained (2). Chlorine ions formed during the further decomposition of this compound (3) can combine with the active phase Ni (4), giving various types of compounds with Ni. The presence of such compounds in the catalyst I evidenced by NiCl2− ion emission detected by TOF–SIMS. In addition, chlorine ions may also be formed as a result of bond breaking between aluminum and chlorine (5). During the mixed methane reforming process, the Al–Cl bond may break and the chlorine ions formed in this way may diffuse from the bulk of the catalyst to its surface, where it combines with nickel (4).The research presented in this paper allows us to propose the mechanism of poisoning the catalytic surface with chlorine . During 3 is La2O3 becomes a component of the catalytic support (6). Residual chlorine associated with nickel, aluminum, or lanthanum can be removed from the catalytic system in the form of hydrogen chloride, which is formed by the reaction of chlorine with hydroxyl groups (7) present on the support surface. However, this process does not eliminate chlorine from the catalyst. The temperature of the mixed methane reforming process (750 °C) is also too low to completely remove chlorine from the catalytic bed.The final decomposition product of LaCl3 does not decompose completely up to the temperature of 750 °C, and the resulting chlorine combines with the remaining components of the catalytic system at the stage of preparation, calcination, or reduction. Finally, the TOF–SIMS analysis showed catalysts based on LaCl3 precursor after the reduction process, showed significant poisoning of the system with chlorine. The result of this work is the proposed mechanism of surface poisoning with chlorine from the catalytic precursor. Based on the obtained results it cannot be recommended to apply chloride precursors for the preparation of catalytic systems.In the above work, the influence of the catalytic support precursor on the activity of nickel catalyst in the mixed methane reforming process was investigated. TPSR tests carried out in a helium atmosphere showed that in the temperature range of 25–900 °C, chlorine is removed from the system in the form of hydrogen chloride, however, this is not possible with 100% efficiency. The conducted TG–DTA tests showed that LaCl


Aspergillus fumigatus is an opportunistic human fungal pathogen, capable of causing invasive aspergillosis in patients with compromised immune systems. The fungus was long considered a purely asexual organism. However, a sexual cycle was reported in 2009, with methods described to induce mating under laboratory conditions. The presence of a sexual cycle now offers a valuable tool for classical genetic analysis of the fungus, such as allowing determination of whether traits of interest are mono‐ or poly‐genic in nature. For example, the sexual cycle is currently being exploited to determine the genetic basis of traits of medical importance such as resistance to azole antifungals and virulence, and to characterize the genes involved. The sexual cycle can also be used to assess the possibility of gene flow between isolates. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.A. fumigatus and for inducing sexual reproduction between compatible MAT1‐1 and MAT1‐2 isolates of the species. The unit also provides working methods for harvesting sexual structures, isolating single‐spore progeny and confirming whether sexual recombination has occurred. © The Authors. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.This unit describes protocols for culturing of  Aspergillus fumigatus is a very common environmental fungus, often isolated from air samples and from rotting vegetation. One reason for the success of the species is the ability to produce prolific numbers of asexual spores  ascomycete fungi including Aspergillus species, in which mating‐type identity is determined by the presence of MAT1‐1 or MAT1‐2 family mating‐type genes  pathogen. Follow all appropriate guidelines and regulations for the use and handling of pathogenic microorganisms. See Current Protocols article  (MAT1‐1) and AFIR928 (=47‐55) (MAT1‐2) of Sugui et al. MAT1‐1 and MAT1‐2 strains from the study of O'Gorman et al. Experience has shown that isolates of Aspergillus fumigatus can be maintained through serial culture on a variety of solid media . Alternatively, a multiplex PCR assay can be performed to determine the mating type of the isolates, based on the protocol of Paoletti et al. A. fumigatus used, DNA extraction can be performed following the guidelines of the Wizard genomic DNA purification kit (Promega).In order to perform a sexual cross between two isolates of 50 ng template DNAPrimers AFM1, AFM2, and AFM3dNTPsTaq DNA Polymerase kit (Thermo Scientific) or another suitable enzymeRed Hot Nuclease‐free water1.5% (w/v) agarose gel1× Tris‐acetate‐EDTA buffer solutionEthidium bromide100‐bp DNA ladderWizard genomic DNA purification kit (Promega) or similarThermal cycler for PCR1A. fumigatus isolate being tested; 50 ng of primer AFM1; 50 ng of primer AFM2; 100 ng of primer AFM3; 200 µM of each dNTP; 1 U of Red Hot DNA Polymerase; 1× Red Hot DNA polymerase reaction buffer; and made up to 25 µl with nuclease‐free water. The details of the primers used are shown in Table The reaction volume for the multiplex mating‐type assay is 25 µl, containing: 50 ng template DNA of the 2The PCR cycle parameters are as follows:3The products of this multiplex PCR assay can then be visualized using gel electrophoresis (1.5% w/v agarose gel in 1× Tris‐acetate‐EDTA buffer) stained with ethidium bromide (0.5 µl/ml). The amplicon size can then be estimated using a 100‐bp DNA ladder.The expected product size of MAT1‐1 isolates is 834 bp, while MAT1‐2 isolates have an amplicon size of 438 bp.Basic Protocol 3A. fumigatus isolates helps to ensure maximum number of cleistothecia are formed. Note that it is recommended to include a control cross between known fertile mating strains in addition to crosses with new test isolates.Once mating type has been determined and two isolates of different mating type have been chosen for the sexual cross, the use of the following protocol for the inoculation of the two complimentary 5 conidia ml−1) of each isolate of A. fumigatusSpore suspensions Class II sterile hood (use in steps 1 to 3 below)Parafilm (or Nescofilm) to seal petri dishes30°C incubator in darkness15 conidia ml−1) in 0.05% Tween 80 from 7‐ to 10‐day‐old grown cultures—using the 10‐µl inoculation loop and sterile 0.05% Tween 80 solution with spore counting by a hemacytometer method or similar  onto the oatmeal agar surface ∼4‐cm apart and perpendicular to aliquots of conidia of the opposite mating type. It is useful to keep a record of which mating partners are inoculated at the defined points, using for example red/blue marks or numbers  and incubate inverted for 3 month at 30°C in complete darkness. Best results are obtained when plates are incubated in single depth rather than being stacked on top of each other.4Periodically examine the cultures over the course of 3 months to ensure the oatmeal agar does not dry out .Basic Protocol 4A. fumigatus sexual cycle. Note that cleistothecia may be submerged under asexual conidiophores and hard to detect by eye. Inspection under a dissecting microscope is therefore often necessary to identify the cleistothecia, and the careful use of dissecting needles to tease apart tissues in the barrage zone can reveal the presence of cleistothecia that are not immediately apparent.After the 3‐month incubation period, examine each sexual cross for production of cleistothecia, visible as white‐cream colored hyphal spherical structures . Typically, these will appear at the barrage zones between two complementary mating partners, and may be scattered individually or group in small clusters Figs. A‐C. ThesFurthermore, if it is necessary to accurately count the number of cleistothecia then the use of a “hoovering” technique is recommended , and crush the cleistothecia in the 100 µl of 0.05% Tween 80. Ideally 5 to 10 cleistothecia will be used at this stage, although a minimum of one cleistothecia is possible.5Adjust the volume of the 2‐ml microcentrifuge tube, adding 1.9 ml of 0.05% Tween 80.6Vortex the solution for 1 min in order to ensure all the ascospores have been released and asci sufficiently disrupted.7Heat for 1 hr at 70°C to kill remaining conidia and mycelial tissues.8During this time, pour 25 ml of 2% malt extract agar (MEA) plates ensuring enough are poured to allow for triplicates of each ascospore solution.9Spread plate aliquots of 100 µl of heat‐treated ascospores onto 2% (w/v) malt extract agar (MEA) plates and incubate for 36 hr at 28°C .CAUTION: When isolating cleistothecia from A. fumigatus sexual crosses, wear a safety mask to minimize the risk of inhalation of conidia and avoid air currents that might cause conidia to become airborne.Basic Protocol 5After 36 hr incubation, the ascospores will have begun germinating. This protocol will describe isolation procedures to enable single ascospore progeny to be isolated for further studies.Plate with germinating ascopores  MEA or ACM plate.4Incubate at 28°C in darkness or diffuse light until fully grown.Basic Protocol 6A. fumigatus have been isolated, it is often valuable to validate that sexual recombination has occurred. Various methods are available, but a relatively straightforward method is to perform DNA fingerprinting of the offspring using random amplification of polymorphic DNA (RAPD‐PCR), as described by Murtagh, Dyer, McClure, and Crittenden .Once individual ascospore progeny from the ittenden . For eac0.1 to 1 ng genomic DNA from each isolate ascospore10 base‐pair RAPD primerdNTPsDyNAzyme II DNA polymerase kit (Thermo Scientific) containing:DyNAzyme II DNA polymerase1× DyNAzyme II DNA polymerase bufferNuclease‐free water1.5% (w/v) agarose gel10× Tris‐boric acid‐EDTA buffer solutionEthidium bromide1‐kb DNA ladder, optionalWizard genomic DNA purification kit (Promega) or similarThermal cycler for PCR1A. fumigatus sexual recombination are shown Table The reaction volume for the RAPD‐PCR assay is 25 µl, containing: 0.1 to 1 ng template DNA from ascospore progeny (note the relatively low amount of DNA template); 50 µmol of a single 10‐base‐pair primer; 500 µM of each dNTP; 1 U of DyNAzyme II DNA polymerase; 1× DyNAzyme II DNA polymerase buffer; and adjusted to 25 µl with nuclease‐free water. Details of recommended primers for validation of 2The PCR cycle parameters are as follows:3The products of the RAPD‐PCR assay can be visualized using gel electrophoresis (1.5% w/v agarose gel in 10×Tris‐boric acid‐EDTA buffer). Due to the high number of products that may be generated from the RAPD‐PCR, electrophoresis gels should be run for an extended period to ensure full resolution of products (approx. 2.5 to 4 hr). For this reason, the gel must be stained with ethidium bromide post‐electrophoresis. Depending on the primer used for the RAPD‐PCR assay, the expected products will vary and product sizes should be estimated using a 1 kb DNA ladder. The parental RAPD profiles are then compared to the progeny RAPD profiles.181.1 g EDTA2O600 ml HAdjust to pH 8 with NaOH2OMake up to 1 liter with dHAutoclave for 15 min at 121°CStore up to 6 months at room temperature−1 malt extract20 g L−1 peptone6 g L−1 agar16 g LAutoclave for 15 min at 121°CStore up to 3 months at room temperature−1 Irish pinhead oatmeal40 g L−1 agar20 g L1 liter tap waterStore up to 3 months at room temperature−1 tris242 g L57.1 ml glacial acetic acid100 ml of 0.5 M EDTA see 2OMake up to 1 liter with dHStore up to 6 months at room temperature− tris108 g L−1 boric acid55 g L20 ml of 0.5 M EDTA see 2OMake up to 1 liter with dHStore up to 6 months at room temperature500 µl TWEEN 802OMake up to 1 liter with dHStore up to 3 months at room temperatureAspergillus fumigatus, based on methods developed by O'Gorman et al. A. fumigatus crosses using the barrage zone method described in Basic Protocol A. fumigatus, but the barrage zone method has proved the most successful in terms of production of cleistothecia. Furthermore, the relatively high temperature resistance of ascospores means that adhering conidia and mycelial tissues can be eliminated by use of the extended 70°C heat shock for 1 hr, which is very advantageous to select for just sexual progeny. The presence of high‐temperature resistant ascospores is only seen in certain Sections of the Aspergilli, such as those with Neosartorya teleomorphs  and quantitative trait loci (QTL) to identify defined genes which contribute to a particular trait.The sexual cycle in A. fumigatus. First, the use of control strains of known fertility which have not been subject to extended vegetative sub culture is recommended. Second, the use of triplicate (or more) repeat plates for each sexual cross is recommended as there can be inherent variability between sexual crossing plates. Third, periodic checking of the sexual crosses during incubation at 30°C is essential for success. If the sealing film used to seal the plates breaks during the three‐month incubation period, the oatmeal agar will dry out and result in a failed sexual cross. Ideally plates are also incubated inverted without stacking in the incubator.There are various critical components to ensure success of sexual mating in 1.Aspergillus species  are used in the author's laboratory.4.Some sexual crosses might exceptionally require more than 3 months for completion. It is recommended to incubate crossing plates for at least 6 months in the dark at 30°C before disposal of plates, to allow for possible delayed/late development of cleistothecia.If sexual development fails to occur when the user performs a sexual cross, this may be due to a number of reasons:After performing the protocol described in this unit, the user should obtain a number of cleistothecia from which ascospores can be isolated.MAT1‐1 genotype and 438 bp if the isolate is a MAT1‐2 genotype.The multiplex mating‐type assay is expected to yield PCR product sizes of 834 bp if the isolate is a The user should expect cleistothecia production primarily at the barrage zone of each sexual cross. Cleistothecia range in size from ∼200 to 600 µm and appear initially a white color, then becoming cream to yellow on aging. If mature, it should be possible to easily pick these sexual structures from the sexual cross using a fine point needle. However, it is important to stress that cleistothecia, even if present, might be hard to detect as they can be immersed under layers of asexual conidiophores. Therefore, the use of a dissecting microscope is needed to detect cleistothecia and judicious use of dissecting needles to tease apart the area of the barrage zone, together with hoovering of the surface of crossing plates (if necessary) as described above.After 36 hr incubation of the ascospore solution, the user should expect to see germinating fungal colonies on the 2% MEA plate. Once the individual ascospores have been isolated, it should be straightforward to establish a single‐spore derived fungal culture.If sexual recombination has occurred, the RAPD‐PCR profiles will be expected to show a mixture of PCR products in the progeny derived from the fingerprint patterns seen in the RAPD‐PCR profiles of the two parents.A. fumigatus crosses must be considered as that is the most time‐consuming protocol within the unit. Generally, the total time to perform the whole unit is approximately 3.5 months, although some crosses can exceptionally require incubation for at least 6 months.The time considerations of this unit vary throughout each protocol depending on how many sexual crosses the user wishes to perform and how many samples are isolated from the germinating ascospores. However, the 3‐month incubation time of the


Photoelectron spectraover a range of photon energies show the characteristic absence oflow kinetic energy photoelectrons expected for dianions as a resultof the repulsive Coulomb barrier (RCB). Vertical detachment energiesof ∼1.6 and ∼1.9 eV and minimum RCBs of ∼1.2and ∼1.3 eV are reported for [Pt2I6]2– and [Pt2I8]2–, respectively. Both of the diplatinum halides exhibit three directdetachment channels with distinct anisotropies, analogous to the previouslyreported spectra for PtI2– and PtI–, suggesting a platinum-centered molecular core thatdominates the photodetachment. Additionally, evidence for two-photonphotodissociation and subsequent photodetachment channels producingI– are observed for both dianions. Finally, an unexplainedfeature is observed at photon energies around 3 eV, whose origin isconsidered. Our work highlights the complex electronic structure ofthe heavy platinum-halide dianions that are characterized by a densemanifold of electronic states.Photoelectron spectroscopyhas been used to study the electronicstructure, photodetachment, and photodissociation of the stable diplatinumiodide dianions [Pt Here, webuild on these small platinum halides and consider the isolated diplatinumiodide dianions [Pt2I6]2– and[Pt2I8]2–. For these molecules,there are outstanding questions concerning how the larger and morepolarizable iodine and the presence of two excess electrons, as wellas the possibility of a platinum–platinum bond, might affectthe electronic structure and photochemistry. To answer these questions,we present a photoelectron imaging study of [Pt2I6]2– and [Pt2I8]2–.Platinum halides have complex electronicstructures and exhibitunusual bonding, resulting in very high electron affinities (EA),high formal oxidation states on the platinum core, and behavior assuperhalogens.13 Typically the RCB manifests in the photoelectron spectra of polyanionsby a characteristic low electron kinetic energy (eKE) cutoff, belowwhich no electrons can be directly emitted. The location of this cutoffcorresponds to the minimum height of the RCB. Photoelectron imagingalso allows the photoelectron angular distribution (PAD) to be measured.The PAD can encode information about the molecular orbital from whichthe electron is ejected;14 however, thiscan be challenging to interpret for dianions where the outgoing electroninteracts with the resultant anion and instead provides a measureof the RCB anisotropy.17A universal aspect of the electronic structure of polyanionsisthe presence of a repulsive Coulomb barrier (RCB) that results fromthe interplay of long-range repulsive forces and short-range attractiveforces.4]2–, [PtBr4]2–, [PtCl6]2–, and [PtBr6]2– by Wangand co-workers.19 Both [PtCl4]2– and [PtBr4]2– are metastable while[PtCl6]2– and [PtBr6]2– are stable with respect to electron loss.7 Photoelectron spectroscopy and electronic structurecalculations have also been performed on the diplatinum dianion [Pt2(μ-P2O5H2)4H2]2–, which indicated a square-planargeometry of ligands around each platinum atom with a Pt–Ptbond, and reported an experimentally measured adiabatic detachmentenergy (ADE) of 2.2 eV and a minimum height of the RCB of 3.5 eV.20 Recently, we used photoelectron spectroscopyat a range of photon energies to study the structure, electron loss,PADs, and photodissociation dynamics of the smallest platinum iodides,PtI2– and PtI–.21 The photoelectron spectra for PtI2– and PtI– were very similarto each other and to the previously studied PtCl2–,22 consisting of three direct detachmentpeaks over a range of ∼1 eV, with distinct anisotropies, indicatingphotodetachment from a localized Pt–X molecular core. Here,we use a similar methodology to study the photodetachment and photodissociationdynamics of [Pt2I6]2– and[Pt2I8]2– as well as reportthe PADs. Strong correlations are seen between the photoelectron spectraof the diplatinum iodide dianions and the diatomic and triatomic platinumiodide anions, suggesting that the electronic structures of all theplatinum iodide species studied to date, whether anionic or dianionic,are similar to the character of the small Pt–I molecular core.Over a number of years, photoelectron spectroscopyhas been performedon the platinum halide dianions 2– and [Pt2I8]2– in this paper. Relativisticeffects,the large contribution and complexity of spin–orbit coupling,and an abundance of electronic states motivated us to not performsuch calculations on the simpler PtI2– and PtI– as we had little confidence in the results.In the present case, electronic structure calculations would be evenmore challenging as the molecules are larger, may contain metal–metalbonds, and have an extra excess electron.Electronic structure calculations were not attemptedfor [Pt2I6]2– and [Pt2I8]2– using nanosecond(ns) laser pulses withphoton energies, hν = 2.8–4.2 eV. Allof the photoelectron spectra are reported on an eKE and electron bindingenergy (eBE) scale, where eBE = hν –eKE. Each spectrum is normalized to the most intense feature withinthat spectrum. From the PADs, an anisotropy parameter (−1 ≤β2 ≤ 2) can be extracted for each spectralfeature.29 Strong similarities are seen between thephotoelectron spectra for [Pt2I6]2– and [Pt2I8]2–, with directphotodetachment and two-photon photodissociation and photodetachmentchannels observed in both cases. The spectra will be reported here,and the implications for the electronic structure and the photochemistryof the diplatinum iodide dianions will be discussed in the followingsection.Photoelectronspectra were recorded for [Pt2I6]2– recordedfrom hν = 2.8–4.2 eV, at 0.2 eV intervals.The identity of the ion was determined by its time-of-flight indicatinga mass-to-charge ratio of m/z =576 amu in combination with the spectral characteristics of a polyanion.On the basis of the natural isotopic abundance of platinum, isotopologueswith m/z between 571 amu ([190Pt2I6]2–) and 579amu ([198Pt2I6]2–) are expected, where 576 amu ([195Pt2I6]2–) is the most abundant m/z, but individual isotopologues are not resolvedin the mass spectra.hν > 3.2 eV with eBE =3.06eV (blue), (B) a sharp peak for hν < 3.0eV with eBE = 2.62 eV on a broader background (red), and (C) a broadercollection of peaks at higher eKE, which increase in structural complexityand relative intensity as the photon energy increases (green). PtI3– is isobaric with [Pt2I6]2–, meaning it may also be present in themass-selected ion packet. However, the presence of the low-eKE cutoffin photoelectron signal, which is a characteristic of a polyanion,and given that the EA of PtCl3– is ∼4.5eV,22 so that there would be insufficientenergy to photodetach PtI3– at the photonenergies used here, indicate that even if it was present, it wouldnot contribute to the spectra shown here.The photoelectron spectra exhibit three distinct features: (A)a sharp peak for 2I6]2–. From the most intenseportion of the first direct detachment feature, we find VDE ∼1.6 eV for [Pt2I6]2–. TheVDE and minimum height of the outer RCB for [Pt2I6]2– are comparable to previously reported valuesfor [Pt2(μ-P2O5H2)4H2]2– of 2.3 and 1.2 eV(extracted from the reported height of the inner RCB), respectively.20As previously noted,the onset of the photoelectron signal correspondsto the height of the outer RCB. From 36 Alternatively, they could arise from a two-photon process throughthe formation of an anionic fragment that is subsequently photodetached.Feature A is a sharp, atomic-like peak with an ADE of 3.06 eV, whichallows us to assign it to detachment of I–. Thisis further verified by the 2P1/2 spin–orbitexcited state of I seen at hv = 4.2 eV. Iodide ispresumably formed via a two-photon process of photodissociation of[Pt2I6]2– followed by photodetachmentof I–. As I– is an anion, thereis no RCB present, and photoelectrons are not restricted by a cutofffor this photodetachment step. The process by which the I– is formed is, however, not clear. It could occur by Coulomb explosionto form I– and [Pt2I5]−, which would have its own ionic RCB to overcome. Thiscan either take place on an excited state or the ground electronicstate of the dianion following some internal conversion process. Thedissociation to form I– over such a broad rangeof photon energies  would be an indication of a very large density of electronicstates of the dianion. Alternatively, I– could beformed by a dissociative photodetachment (DPD) process in which [Pt2I6]−, produced via photodetachment,spontaneously decays to form I– and [Pt2I5]. As discussed above, it is possible that PtI3– is present in the ion beam and able to undergophotodissociation to produce the observed anionic fragments, but thiswould be impossible to distinguish from photodissociation of [Pt2I6]2– using our experimentalapparatus.Features A and B appear below the RCB,where no signal should bepresent. Their appearance could arise from resonant excitation toan excited state from which electrons can be lost by tunneling throughthe RCB.hν = 3.0 eV thereis insufficientphoton energy to photodetach I–, but a sharp featureat low eKE on top of a broad background signal is also observed forthese photon energies (but not at higher hν). This feature again has the appearance of an atomic photoelectronspectrum with an eBE of 2.62 eV. The origin of this feature is unclearas its eBE does not correlate with the electron affinity of any knownatomic element, let alone I or Pt. Potential explanations for thefeature will be explored in the At and below – and PtI2–.21 At hν = 4.0 eV the PAD is characterized byβ2 = −0.9, −0.6, and 1.5 for electronicstates with increasing eBE. Interpreting the PADs following directdetachment of a dianion cannot be done in the same manner as for amonoanion, as the location of the remaining excess negative chargeultimately determines the final PAD and therefore must be accountedfor.16 In the absenceof high-level electronic structure calculations for [Pt2I6]2–, it is difficult to extract anyinformation about the nature of the molecular orbitals from the PAD,other than to say the presence of a number of electronic states withdiffering anisotropy appears to be a characteristic of platinum iodides,as both singly and doubly charged anions.At the highest photon energies studied, up to threedistinct peakswith different PADs are observable above the RCB. These features shiftto higher eKE as the photon energy is increased, suggesting a directdetachment mechanism. The direct detachment features are very reminiscentof the structure of the direct detachment channels of PtIm/z ∼ 703 amu recorded with a nanosecond laser between hν = 3.0–4.2 eV. Given the m/z and that the spectra share many similaritieswith those for [Pt2I6]2–,this ion most probably corresponds to [Pt2I8]2–, which has an expected isotopologue distributionbetween m/z = 698 and 706 amu. Again,three clear features are present: (A) a low-eKE feature attributableto the photodetachment of I– (blue); (B) a sharpfeature on a broad background at eBE = 2.77 eV (red); and (C) a higherenergy broad feature consisting of multiple peaks from direct detachmentof the parent anion (green). In this case the relative intensity ofthe two-photon feature is much larger than the one-photon direct detachmentchannel, at all photon energies. The minimum height of the outer RCBis estimated to be ∼1.3 eV. The VDE is measured to be ∼1.9eV and comparable with the VDEs of [Pt2I6]2– and the previously reported [Pt2(μ-P2O5H2)4H2]2−. Similar to the case of [Pt2I6]2–, PtI4– is isobaricwith [Pt2I8]2– and could bepresent in the ion beam. However, the spectra indicate a dianion andthe EA for PtCl4– and PtF4– are higher than the photon energies used here(EA ≥ 5 eV),37 suggesting that even if present,PtI4– would not photodetach.– fragment, similar to the observation for [Pt2I6]2– . The relativeintensity of feature A to that of C decreases with increasing hν. This may indicate a decrease in the photodissociationor photodetachment cross section in the ionic fragmentation channels,but it is more likely attributed to the direct detachment of the dianionbecoming energetically accessible at the photon energy used. At thehighest photon energy used, there is sufficient energy to photodetachto both spin–orbit states of I, resulting in the pair of sharppeaks separated by 0.95 eV. As before, I– is observedover a very large excitation range, and we do not see evidence ofelectron tunneling through the RCB, although there are clearly excitedstates accessed.38 As PtI4– may be present in the ion beam, it could undergo photodissociationand be the source of the observed I–.The low-eKE feature . In this case, it isunclear whether the feature shifts linearly with hν, as it is only present at one photon energy studied and we notethat it is exceedingly weak. Nevertheless, it has the appearance ofan atomic anion, but, as before, no element has the matching electronaffinity.Similarto [Pt2I8]2–. Similar to the previous platinumiodide species, three electronic states are observed in the spectraat higher hν, but they are difficult to conclusivelydiscern as the spectral width of the feature increases with photonenergy, too. Distinct PADs are observed for the three features presentat hν = 4.2 eV characterized by β2 = −1.0, −0.5, and 1.0 for states with increasingeBE. Similar to [Pt2I6]2–,it is challenging to interpret the PADs for [Pt2I8]2–, although we note that the overall trend ofβ2 < 0, < 0, and > 0 was also observed for[Pt2I6]2–, thus suggestinga similar overall electronic structure.The high-eKE feature, which is strongly affected bythe presenceof the RCB, originates from direct photodetachment of [Pt2I6]2– and [Pt2I8]2– will be comparedand contrasted with each other and with previouslystudied platinum halides and other platinum clusters. The photoelectronspectra for [Pt2I6]2– and[Pt2I8]2– exhibit a numberof similarities including multiple direct detachment features withstrongly anisotropic PADs  in [Pt2I6]2– and +3 (d7)in [Pt2I8]2–. The constituentPtI3– and PtI4– fragments are electron-deficient with 14 and 15 electrons, respectively,in contrast to the 18-electron count of many stable transition metalcomplexes. Dimers are likely to form to stabilize the electron-deficientfragments, either by the formation of a platinum–platinum bondor via bridging iodine ligands. Given that in the solid phase [Pt2I6]2– and [Pt2I8]2– demonstrate a preference for platinumcores linked by bridging iodine atoms, as determined via X-ray diffractionof solid state crystals with various counterions, a similar structuremay be expected in the gas phase, too.40 Additionally,the crystal structures of the dianions indicate square-planar andoctahedral coordination geometries of iodine ligands around the platinumatoms, which are also likely in the gas phase.40 While photoelectron spectroscopy is a powerful tool for studyingthe electronic structure of molecules, it is less well-suited to obtainstructural information, especially in the absence of calculations.Infrared spectroscopy would be more suitable for studying the nucleargeometry of these diplatinum dianions in the gas phase.Assuming the negative charges are localized on the iodine ligands,then the oxidation state of platinum is +2 (d2I6]2– and [Pt2I8]2– are similarin magnitude to each other (1.6 and 1.9 eV) but significantly smallerthan for PtI2– (3.5 eV). This differencebetween the dianions and anions is due to the larger electron–electronrepulsion in the dianions. The marginally higher RCB observed for[Pt2I8]2– compared to [Pt2I6]2– (∼1.3 and ∼1.2eV) is somewhat unexpected given the larger size of [Pt2I8]2–, which may be expected to facilitategreater separation of the excess charges and reduce the Coulomb repulsionwithin the molecule. However, this type of argument is strongly dependenton the geometries of the dianions, which are not determined here.The VDEs and minimum heights of the outer RCBs we record for [Pt2I6]2– and [Pt2I8]2– are similar to values previously recordedfor [Pt2(μ-P2O5H2)4H2]2– of 2.3 and 1.2 eV(inner RCB is 3.5 eV), respectively.Theobserved VDEs for 2– and [Pt2I8]2– to the smaller anions suggests that these are highly symmetricalmolecules, where direct detachment is occurring from a small molecularcore. This result may indicate that the dimers are linked via bridgingiodides similar to the known solid state crystal structures,40 rather than a platinum–platinum bond, due to the strong spectralsimilarities between the diplatinum iodide dianions and the platinumiodide anions. However, it should be noted that this similarity isalso evidence of the limited scope photoelectron spectroscopy hasto unravel the full geometric structure of the diplatinum dianions,as the three observed transitions can arise from just a single Pt–Ibond.The motif of three sharppeaks in the direct detachment featurewith an overall spectral width of ∼1 eV and with differentanisotropies is present in both of the dianions studied here as wellas the previously investigated PtI2I6]2– and [Pt2I8]2–. It is verychallenging to perform such calculations of small platinum halides,such as PtI2– and PtI–, due to the large spin–orbit coupling of both Pt and I aswell as the substantial relativistic effects that need to be accountedfor.21 On top of this, the diplatinum iodidedianions have the challenges of containing more atoms and the needto accurately account for the presence of two excess electrons withinthe dianion’s molecular framework. A simple d-block model canbe used to attempt to understand the nature of the highest energyMOs by considering symmetry.41 However,spin multiplicities and spin–orbit coupling, particularly J–J coupling which is used for Pt,complicate the picture greatly by adding many additional states, makingeven a qualitative interpretation challenging. Hence, we prefer tonot endeavor into such speculation here.As noted previously, we have not attempted electronicstructurecalculations for 2– and[Pt2I8]2– have been studiedby using frequency-resolved photoelectron imaging. Direct detachmentchannels are observed as a band of three peaks, with distinct anisotropiesand a spectral width of ∼1 eV, which are strongly reminiscentof the photoelectron spectra of PtI2– and PtI–, suggesting that the highest energy MOs,which contribute to the photodetachment dynamics, are associated withPt–I bonds. Photodissociation of the diplatinum dianion toproduce I–, which is photodetached in a two-photonprocess, is observed for both species studied and dominates at thelower photon energies investigated. An additional two-photon atom-likefeature is observed at the lowest photon energies studied, but theorigin is unclear. Overall, we show that the photochemistry of thediplatinum iodide dianions is very rich with differing photodetachmentand photodissociation channels. While the electronic structure isvery complex and would require electronic structure calculations thataccount for relativistic effects, aspects are also rather simple andcan be correlated to that of the Pt–I– photodetachment.We hope our work will stimulate computational interest in these richsystems to further understand their electronic structure and uncovertheir geometric structure.Theelectronic structure, photodetachment, and photodissociationdynamics of [Pt


It was characterized by X-ray powder diffraction, thermal analysis, and impedance and vibrational spectroscopy. X-ray diffraction data confirmed formation of a single phase material which crystallized at room temperature in the hexagonal system (P63mc space group). DSC showed the existence of two phase transitions at 413 K and 430 K. Electrical conductivity was measured in the temperature and frequency ranges of 390 K to 440 K and 40 Hz to 110 MHz, respectively. Nyquist plots revealed the existence of grains and grain boundaries that were fitted to an equivalent circuit. AC conductivity plots were analyzed by Jonscher's power law. Variations in the “s” values indicated that CBH models describe the conduction mechanism in regions I and II. Temperature dependence of Raman spectra showed that the most important changes were observed in the cationic parts ([(C2H5)4N]+). The activation energy value obtained from the line width decreased which indicated an order–disorder model.The compound, tetraethylammonium tetrachloroferrate [(C 2H5)4N]FeCl4 at different temperature.Complex impedance spectra of [(C Obtaining such a material in the form of solids with a continuous lattice was found to be very complicated. However, a material with a multifunctional character can be obtained by building up hybrid solids formed by two lattices consisting of organic and inorganic parts. Much attention has been paid to organic–inorganic hybrid materials due to the possibility of each moiety contributing its own characteristic properties.5 in their molecules. Compounds containing tetrahalogenferrate(iii) units may also be used as attractive magnetic materials.14,15 Moreover, it was found that some of the iron(iii) complexes have been used in bioinorganic chemistry as substances for synthesizing model compounds, such as [Fe2S2Cl4]2−.16Special attention is paid to compounds based on iron. Owing to the presence of the high-spin d2H5)4N]FeC14 crystals, and a description of basic information about their properties. This compound is of interest due to the presence of Fe(iii) in a tetrahedral coordination structure that mainly provides the existence of magnetic, electric, and elastic anomalies.17 At room temperature, the system belongs to the hexagonal system (space group P63mc) with four formulae per unit cell, which has dimensions of a = b = 8.198 Å, c = 13.183 Å.18With this aim, we wish to report the growth of [ and [N(C2H5)4]Cl  was performed in aqueous solution. After few days, yellow prismatic crystals were obtained by slow evaporation at room temperature. The sequence of the chemical reaction is the following:Mixing a stoichiometric molar ratio of FeCl2.2α (λ = 1.5405 Å), the XRD pattern was recorded in a wide range of Bragg angles (10° ≤ 2θ ≤ 60°). Structural refinements ware carried out by the Rietveld refinement method.19 Differential scanning calorimetry, DSC, was executed with a Perkin Elmer DSC-7 instrument in a temperature range from 300 K to 470 K with a 5 K min−1 rate. Thermogravimetric analysis (TGA) was performed with an ATG-Q500 SETARAM in a heating process from room temperature up to 772 K with a heating rate of 10 K min−1.Phase purity and homogeneity were checked using X-ray powder diffraction analysis. Using a Phillips PW 1710 powder diffractometer operating with CuK2H5)4N]FeCl4 powder was pressed at 5 t cm−2 ton pressure, forming a circular disc with a 1.1 mm thickness and 8 mm diameter. Measurements were executed in the frequency range of 40 Hz to 110 MHz using a 4294A impedance analyzer. The measurements were carried out under an excitation voltage of 50 mV. In the present study, we found that after several tests our pellet became softer after 430 K, which proved that these organic–inorganic crystals of tetraethylammonium tetrachloroferrate show plastic behavior at high temperature.6 Therefore, the sample is not in the form of an electrical dipole, which shows that measurement after 430 K is not possible.To study the electrical proprieties, the [(C2H5)4N]FeCl4 was recorded at room temperature in the frequency range of 500–3500 cm−1.Using a Perkin Elmer FT-IR 1000 spectrophotometer, the infrared spectrum of [4N]FeCl4. The Rietveld refinement was performed using the FULLPROOF software program. The circles symbolize the experimental data and the line presents the simulated pattern. The purity of the studied compound was proved and the reflection peaks were indexed in the hexagonal system with the P63mc space group. The corresponding lattice parameters were found to be: a = b = 8.218 Å, c = 13.203 Å and the cell volume was V = 772.2 Å3. The quality of the refinement was evaluated through the goodness of fit where χ2 = 1.23. The values of the reliability factors obtained from the refinement are Rωp = 13.5, Rp = 18.5 and Rexp = 12.04 and the fitted parameters were found to be in a good agreement with those in the literature.183.22H5)4N]FeCl4. The DSC curve was recorded with a heating scan at 5 K min−1. The calorimetric measurement showed that the compound under investigation undergoes discontinuation of two phase transitions at T1 = 413 K and T2 = 430 K. The characteristic dynamical values of these phase transitions are listed in S = R ln(Ω)), where Ω is the rapport number of distinguishable orientations allowed in the high- and the low temperature phases (N1/N2).From the Boltzmann equation, , which reveals that these two phase transitions are not purely “order–disorder”.20The obtained values of The thermogravimetric analysis (TGA) curve in 3.321Impedance spectroscopy is one of the most suitable techniques to investigate electrical conductivity and to analyze the charge transport processes in grains, grain boundaries, and electrode effects in materials in terms of thermal and frequency ranges.22 In addition, they are centered below the abscissa axis indicting that the relaxation process in the material is of a non-Debye type.23 . The Nyquist diagram is a perfect semicircle centered on the abscissa axis but there are other cases where all dipoles do not have the same relaxation time (distribution of relaxation time). There are several empirical models derived from the Debye equation that correctly describe these types of relaxations including the Cole–Cole model25–27 and the Nyquist plot described by a flattened arc with its center located below the real axis on a line deviated from the angle of (1 − α)π/2 where α describes the interactions between dipoles.R1 and fractal capacity CPE1 in series with a parallel combination of grain boundary resistance R2 and fractal capacity CPE2. The constant phase element (CPE) impedance is given by the following equation:28Q presents the capacitance value of the CPE fractal capacity and α relates to the deviation degree with respect to the pure capacitor value.Nyquist plots were analyzed using Zview Software. The best fits were obtained using an equivalent circuit inset  realizedZ′) and imaginary (−Z′′) parts linked to the equivalent circuit were calculated according to the following The theoretical impedance of real (Z′) and imaginary (−Z′′) at various temperatures, are depicted in Z′ decreased, where increases in both frequency and temperature indicated an increase in AC conductivity of the sample. At frequencies higher than 106 Hz, the coincidence of the impedance (Z′) at all temperatures showed a possible freeing of space charge29 whereas, the Z′′ peak maximum decreased with a rise in temperature. The peak frequency ωmax shifted to higher values and the later reflected a non-Debye type relaxation.30The frequency dependence of the impedance of real (Q1 and Q2) are in the range of picofarads (pF) and nanofarads (nF), respectively, implying a single semicircle response is from grain interiors and grain boundaries. The values of α vary in the range of 0.81–0.99 showing a capacitive behavior of the fractal phase CPE.3129e and S are the thickness and area of the sample, respectively, and R1 is the bulk resistance. The dependence of ln(σgT) versus 1000/T is presented in σg decreased as temperature decreased. This indicated that electrical conduction in the material is a thermally activated process and was fitted well by the Arrhenius relation as described by σ0 is the pre-exponential factor, Ea is the activation energy, and kB is the Boltzmann constant.Electrical conductivity spectroscopy is a well-founded method for characterizing hopping dynamics of the charge carriers. Based on the equivalent circuit parameters, grain conductivity is expressed according to the following expression:T1 (413 ± 5 K) are Ea (I) = 0.74 eV in region I and Ea (II) = 1.13 eV in region II. The observed variation in the activation energies between the two temperature domains can be explained by movement of the cationic and anionic parts with temperature.32 However, the discontinuity at 413 ± 5 K agrees with the phase transition observed in the DSC measurements.The activation energies obtained by the linear fit at 3.42H5)4N]FeCl4 is shown in The variation of AC conductivity with angular frequency for [4N]FeCl4, different theoretical models proposed by Long et al. were used to correlate the conduction mechanism of AC conductivity with the predicted exponent s(T) behavior.34–37 These different models are: QMT, the quantum mechanical tunneling model, OLPT, the overlapping large polaron tunneling model, NSPT, the non-overlapping small polaron tunneling model, and CBH, the correlated barrier-hopping model. Comparing the obtained results with the extracted exponent s temperature dependence behavior (2H5)4N]FeCl4 was best interpreted with the correlated barrier hopping (CBH) model in region I and II.In order to identify the predominant conduction mechanism for InBr4,42 [(C2H5)4N]SbF6,43 [(C2H5)4N]SbCl6,44 [(C2H5)4N]2CoCl4,45 [(C2H5)4N]2HgI4, [(C2H5)4N]Hg3I8,46 and [(C6H5)4P]FeCl4 (The IR and Raman spectra of tetraethylammonium tetrachloroferrate are presented in 4P]FeCl4  and are ν2(FeCl4) and ν4(FeCl4)) are observed at 121 and 142 cm−1, respectively. The strongest Raman band at 335 cm−1 is assigned to the symmetric stretching modes (ν1(FeCl4)), whereas the asymmetric stretching vibration (ν3(FeCl4)) gives the Raman peaks at 379 and 397 cm−1.Symmetric and asymmetric bending vibrations (−1 displays one band (at ca. 3022 cm−1) attributable to the (νas (CH3)) vibration. The Raman and IR bands at 2990 and 2989 cm−1, respectively, are attributed to the CH2 asymmetric stretching mode (νas(CH2)). The IR peak at 2979 cm−1 is assigned to the CH3 symmetric bending mode (δs(CH3)). On the other hand, the symmetric bending mode (δs(CH2)) is observed at 2952 and 2950 cm−1 in the Raman and IR spectra, respectively. The asymmetric bending of CH2 groups (δas(CH2)) is found at 1460 and 1440 cm−1 in the Raman and at 1455 cm−1 in the IR spectra. The CH3 symmetric bending (δs(CH3)) mode appears at 1353 cm−1 in the Raman spectrum. The observed Raman band at 1307 cm−1 and IR band at 1302 cm−1 are assigned to CH2 twitching mode (t(CH2)). The CH3 rocking vibration (ρr(CH3)) is in the Raman spectrum at 1185 and 1008 cm−1 and also as doublet IR bands at 1183 and 1006 cm−1. The asymmetric stretching mode (νas(C–C)) is identified at 1082 cm−1 in Raman and at 1079 in IR, whereas the symmetric stretching mode (νs(C–C)) presents a Raman band at 895 cm−1. The N–C asymmetric stretching vibration (νas(N–C)) is observed at 1022 and at 1033 cm−1 in Raman and IR, respectively, while the symmetric bending modes (νs(N–C)) are located at 665 cm−1 in the Raman spectrum. A strong transmission band appearing in IR near 791 cm−1 and Raman band at 794 cm−1 are assigned to the CH2 rocking vibration (ρr(CH2)). The band related to the CNC skeleton deformation (δs(CNC)) is detected in the Raman spectrum at 554 cm−1.The Raman spectrum above 3000 cm3.6In order to gain more information on the crystal dynamics and on the mechanism involved in the transition, we undertook a vibrational study using Raman scattering between 303 and 428 K.2H5)4N]FeCl4 recorded in three spectral ranges . A deconvolution of all spectra was necessary to follow the temperature dependence of the wavenumber and half maximum. This deconvolution was carried out by means of Labspec software with a combination of two Lorentzian and Gaussian functions.4]− observed between 50 and 400 cm−1. We noticed that this figure indicates weak changes near 418 K where the phase transition has been observed. The line at 121 cm−1 associated with ν2(FeCl4) mode underwent a shift toward high frequency by 2 cm−1, with a half maximum decrease by 5 cm−1. The two bands at 379 and 397 cm−1 attributed to ν3(FeCl4) vanished at the temperature transition.−1 frequency range which issued from the internal modes of the cationic parts. The two bands around 554 and 1185 cm−1 assigned to the δs(CNC) and ρr(CH3), respectively, vanished after the phase transition (418 K), while three bands appeared in the vicinity of 595, 750, and 1528 cm−1 at 418 K. A large change was detected for the peak at 665 cm−1 (νs(N–C)), where it broke into two bands after 418 K. Another important change in the position was observed near 1440 and 1460 cm−1 (δas(CH2)). These two bands merged into a single line at 418 K while the half maximum of them increased to 15 cm−1 above the transition. The bands observed between 2800 and 3200 cm−1, which were assigned to the symmetric and asymmetric vibration of CH2 and CH3 groups, did not change significantly with temperature; their position and half maximum underwent weak changes (a few cm−1) which means that these modes are not directly connected to a phase transition.In 2H5)4N]FeCl4 crystals are due to a phase transition at T = 418 K which is in good agreement with DSC measurements and electrical proprieties. The most pronounced changes were found to be connected with vibration of the cationic part. In order to confirm the main role of the organic part in the phase transition point, we focused our study on the band around 1440 cm−1 associated with the CH2 asymmetric bending mode δas(CH2).Spectral anomalies observed in Raman spectra of the + cation.53 This allows us to conclude that the observed phase transition is related to the reorientation dynamical disorder of the tetraethylammonium cation.The decrease of these values with increasing temperature is explained by the gradual evolution from an ordered state to a disordered phase resulting from an increase of the dynamics [(C4.P63mc space group) was prepared and investigated as a function of temperature and frequency. One phase transition at 413 K was detected by differential scanning calorimetry (DSC). Additionally, Nyquist plots revealed the existence of grains and grain boundaries that were fitted by an equivalent circuit. The AC conductivity spectrum was found to obey Jonscher's power law.Tetraethylammonium tetrachloroferrate with a hexagonal system (s(T) indicated that a correlated barrier hopping (CBH) was the most suitable model for the conduction mechanism. Significant changes of several bands for the internal modes of the organic cation were observed within the phase transition temperature. Temperature dependence analysis of the frequency and the width of the δas(CH2) mode proved that there is an anomaly around T = 418 K, a consequence of an order–disorder phase transition. The decrease of Ea values below the order–disorder phase transition can be understood as a change in the dynamical states of the cation.The temperature dependence of the exponents There are no conflicts to declare.


The “phloroglucinol trick” was used to circumvent two synthetic issues encountered when assembling four EC units, namely, the steric constraint and the formation of the C4−C6 interflavan linkage. As a substructure of the middle EC unit, phloroglucinol enabled the single‐step assembly of two EC units (top and side) through A‐type linkages. The middle EC unit was constructed by conducting a newly developed three‐carbon flavan annulation via a Pummerer/Friedel–Crafts cascade reaction to furnish a trimeric intermediate bearing a thio‐leaving group at C4 position, which allowed the final installation of the bottom EC unit.The first total synthesis of parameritannin A2 ( By overcoming steric constraints, a stereoselective total synthesis of the branched tetramer parameritannin A2 was achieved. As a key step of the approach, a Pummerer/Friedel–Crafts cascade enabled the de novo construction of the middle flavan unit for its regioselective linkage to the bottom flavan unit. This structure contrasts with the linear array of EC units shared by many flavan oligomers, such as procyanidin D (2) and cinnamtannin B2 (3), which differ in the absence or presence of an A‐type double linkage.Parameritannin A2  is an ep1. We envisaged two potential issues in the construction of the branched structure of 1, i.e., 1) the steric constraint in the assembly of three EC units to the middle EC unit and 2) the lack of a reliable approach for the formation of the C4−C6 interflavan bond.In our synthetic studies on oligomeric proanthocyanidins (OPAs), we previously completed the total syntheses of linear‐type OPAs with or without a double linkage4, 5 a1, the top‐middle and middle–bottom connections (pink) involve a C4−C8 bond, for which we could rely on our previously established methods (vide infra). However, the formation of the middle‐side linkage (blue) involved a more challenging C4−C6 interflavan bond (yellow).Among the three interflavan linkages in B, which is generated upon activation with hard and soft Lewis acids of catechin units ORA and SRA that contain oxy and thio moieties as leaving groups, respectively. IAlthough this protocol served as a basis for our OPA synthesis, allowing flexible access to various flavan congeners including scarcely available derivatives, we suspected that it might not be effective in the present context due to the challenging installation of a leaving group at C4 position in intermediates having other benzylic C−H bonds more prone to undergo DDQ oxidation.P′ into sulfoxide Q′, which would be subjected to Pummerer conditions to afford cationic species R′. Finally, the Friedel–Crafts cyclization of R′ would furnish flavan unit T′ bearing a thio‐leaving group at C4 position.Therefore, we resorted to performing an alternative reaction to enable direct access to a dimerization‐ready flavan unit. As shown in Scheme O′ to P′, which we had observed in some substrates having an electron‐rich B‐ring, leading to an SN1 ionization,p‐phenol on the B‐ring using an electron‐withdrawing group (EWG).To prevent the potential stereochemical erosion in the Mitsunobu reaction from anti‐18 as depicted in Scheme S)‐glycidol (13)14 (66 % yield in two steps),15 having a free phenol, which would later be protected using tert‐butoxycarbonyl (Boc) as an EWG. Thus, phenol 1516 was subjected to bromine‐lithium exchange . Amide 14  was added to the resulting aryllithium solution, furnishing ketone 17 in 70 % yield. After protection of the B‐ring phenol in 17 with a Boc group ,4)2 18 with high stereoselectivity (anti/syn=96 : 4). We successfully separated the anti‐18 and syn‐18 diastereomers by silica gel column chromatography.Following this strategy, we synthesized epoxy alcohol nBu3P)anti‐18 and phenol 11, which proceeded with a complete inversion of the stereochemistry to give epoxy ether 19 in 76 % yield 3COH, −10 °C, 72 h]syn‐ and anti‐21 in 71 % and 22 % yield, respectively.Subsequently, we performed the modified Mitsunobu reaction dipiperidine, 21 in hand, we examined the planned cyclization via Pummerer/Friedel–Crafts cascadesyn‐21 with TMSOTf in the presence of Et3N  gave sulfide 23 in 60 % yield instead of the desired cyclized product 22 (run 1).iPr2NEt led to the formation of 22, anaerobic filtration (argon), removal of the volatiles, and lyophilization gave crude 1. Reverse‐phase preparative HPLC1 as an ivory amorphous solid (91 % yield), whose physical data were indistinguishable from the reported data of natural 1 {1H and 13C NMR, IR, high‐resolution MS (ESI),28D=+13  [lit.28D=+12.1 ]}.We then tackled the union of the final EC unit Scheme . The act °C, 2 h)4, 5 a1). The key features include (1) a phloroglucinol trick to circumvent the C4−C6 bond‐forming issue and (2) a de novo construction of the flavan skeleton with a leaving group at C4 position, which served for the final assembly of the bottom EC unit to complete the construction of the branched tetrameric structure. The strategies and tactics presented herein will provide flexible synthetic access to various oligomeric catechins with potential biological activities.In summary, we achieved the first total synthesis of parameritannin A2  should be addressed to the authors.Supporting InformationClick here for additional data file.


A range of isocyanates and an isothiocyanate were investigated. In the case of isocyanates, silyl bonding at oxygen or nitrogen is regioselectively directed by the functional group on the isocyanate and substituents on the silyl moiety. Above all, we find that captured isothiocyanate molecules can be exchanged for isocyanate molecules, indicative of small molecule catch and release. Small molecule catch and release at these Zintl‐derived clusters reveals their potential application as chemical storage materials or as reusable probes.Despite being known for decades the chemical reactivity of homoatomic seven‐atom phosphorus clusters towards small molecules remains largely unexplored. Here, we report that neutral tris(silyl) functionalised heptaphosphane (P Three equivalents of heteroallene can be captured between the Si−P bonds of Zintl‐derived clusters. Silyl coordination at either the nitrogen or chalcogen of the heteroallene can be controlled by tuning the groups on the silyl moiety or functional groups at the heteroallene. It was also found that one captured small molecule can be exchanged for another, evidencing small molecule catch and release at these clusters. This solubility allows for rapid assessment of solution‐state reactivity. While, red phosphorus is a difficult to study heterogeneous material. [P7] cages can be considered molecular models, and perhaps inform what types of functionalised red phosphorus materials can be targeted for chemical storage.The heptaphosphide trianion,  cages are limited  in hydropnictination reactions with carbodiimides and isocyanates.7]3−  with alkynes transferred a [Pn3]− unit to afford 1,2,3‐tripnictolides,− to give the [PCO]− anion.Examples of small molecule activation with . For the amide linkage [RC(=O)NR2] the C−O and C−N bond lengths average 1.225 and 1.358 Å, respectively 3  was prep2. 31P VT NMR studies between −70 to 50 °C revealed no indication of tautomerization; only 2 was observed. 31P SS NMR studies gave resonances too broad to be conclusive. The 29Si SS NMR spectrum was consistent with that collected in the solution‐state and showed no evidence of tautomerization. To investigate if the Me3Si‐group prefers oxygen bond formation and to force tautomerization the reaction mixture was heated at 50 °C, but only decomposition of the cage was observed.Variable temperature (VT) NMR studies and solid‐state (SS) NMR studies were undertaken to probe tautomerization between the imidate and amide moieties of 1 was also treated with one and two equivalents of phenyl isocyanate to isolate the partially inserted products, but only formation of 2 and unreacted starting material could be detected by NMR spectroscopy and XRD studies. This suggests that tris‐insertion is preferred over mono‐ or bis‐insertion of the heteroallene.Compound 1. Treatment of 1 with 4‐bromophenyl isocyanate afforded the related insertion product 3 phenyl isocyanate showed 1H and 29Si NMR spectra consistent with the formation of 4 or 5, respectively, which contains N,O,O‐silyl bonding. Reaction of 1 with p‐tolyl isocyanate or 4‐(methoxy)phenyl isocyanate resulted in formation of compounds 6 or 7, correspondingly. NMR and XRD studies into 6 and 7 revealed that the Me3Si units selectively bonded to the isocyanate nitrogen atoms to give three amide groups. To eliminate the possibility of Si−O bond formation, 1 was reacted with phenyl isothiocyanate and found to give compound 8  Å, C−O 1.217(av) Å; 7: C−N 1.356(av) Å, C−O 1.212(av) Å; 8: C−N 1.349(av) Å, C−S 1.662(av) Å). Finally, p‐toluenesulfonyl isocyanate (p‐toluenesulfonyl=tosyl) was found to insert into the P−Si bonds of 1 with selective Si−O bond formation to give three imidate groups  diminishing in intensity and new resonances being observed between 12 and 32 ppm. The silyl regioselectivity upon insertion was determined using 1H and 29Si NMR spectroscopy, Figure 29Si NMR signals. In the case of 2, 6–9 silyl regioselectivity was further validated by single‐crystal XRD studies. As electron‐withdrawing groups are introduced on the isocyanate aromatic ring, upon insertion, the silyl group prefers coordination to the oxygen atom.Formation of insertion products 10–12 were prepared where methyl groups on Si are sequentially replaced with phenyl groups  of the silyl group increases in the order 1<10<11∼12. Consistent with Lewis acidity at the Si centre increasing as methyl groups are replaced with phenyl groups. [P7] bonded silyl groups also showed smaller FIA values when compared to traditional Lewis acids, such as B(C6F5)3, SbF5, and [Me3Si]+ phenyl isocyanate, and p‐tolyl isocyanate phenyl isocyanate under similar conditions showed no reaction. It was also found that the inserted phenyl isocyanates of 2 showed no exchange with phenyl isothiocyanate. Additional efforts to exchange the capture isocyanates of 2, 3, and 5 with another isocyanate required long reaction times at elevated temperatures and led to significant cage decomposition.To probe reversible binding of the captured heteroallenes exchange reactions were undertaken. It was found that when compound y Scheme . From th8  FLP small molecule activations.2. Future investigations are focused on CO2 capture with Zintl clusters and the subsequent reduction chemistry of the activated heteroallenes.In conclusion, we report on the capture of isocyanates and an isothiocyanate between the Si−P bonds of tris(silyl) functionalised heptaphosphide clusters. In the case of isocyanates, it was found that both O−Si and N−Si bond formation was possible. Preferential oxygen bonding was observed when aromatic groups were incorporated on the silyl unit or when isocyanates featuring electron‐withdrawing groups were utilised. Further, it was found that in the case of The general information, experimental procedures, characterisation data, and computational details are available in the Supporting Information.2), 2101381 (for 6), 2101382 (for 7), 2101376 (for 8), 2101377 (for 9), 2101378 (for 10), 2110872 (for 11), 2101374 (for 15), and 2101380 (for 18)2101379  should be addressed to the authors.Supporting InformationClick here for additional data file.