Thermodynamic Modulation of Dihydrogen Activation Through Rational Ligand Design in GeII-Ni0 Complexes.

A family of chelating aryl-functionalized germylene ligands has been developed and employed in the synthesis of their corresponding 16-electron Ni0 complexes (PhiPDippGeAr·Ni·IPr; PhiPDipp = {[Ph2PCH2Si(iPr)2](Dipp)N}-; IPr = [{(H)CN(Dipp)}2C:]; Dipp = 2,6-iPr2C6H3). These complexes demonstrate the ability to cooperatively and reversibly activate dihydrogen at the germylene-nickel interface under mild conditions (1.5 atm H2, 298 K). We show that the thermodynamics of the dihydrogen activation process can be modulated by tuning the electronic nature of the germylene ligands, with an increase in the electron-withdrawing character displaying more exergonic ΔG298 values, as ascertained through NMR spectroscopic Van't Hoff analyses for all systems. This is also shown to correlate with experimental 31P NMR and UV/vis absorption data as well as with computationally derived parameters such as Ge-Ni bond order and Ni/Ge NPA charge, giving a thorough understanding of the modulating effect of ligand design on this reversible, cooperative bond activation reaction. Finally, the utility of this modulation was demonstrated in the catalytic dehydrocoupling of phenylsilane, whereby systems that disfavor dihydrogen activation are more efficient catalysts, aligning with H2-elimination being the rate-limiting step. A density functional theory analysis supports cooperative activation of the Si-H moiety in PhSiH3.

Probe the Dynamic Adsorption and Phase Transition of Underpotential Deposition Processes at Electrode-Electrolyte Interfaces.

Electrochemical scanning tunneling microscopy (EC-STM) and electrochemical quartz crystal microbalance (E-QCM) techniques in combination with DFT calculations have been applied to reveal the static phase and the phase transition of copper underpotential deposition (UPD) on a gold electrode surface. EC-STM demonstrated, for the first time, the direct visualization of the disintegration of (√3 × âˆš3)R30° copper UPD adlayer with coadsorbed SO42- while changing sample potential (ES) toward the redox Pa2/Pc2 peaks, which are associated with the phase transition between the Cu UPD (√3 × âˆš3)R30° phase II and disordered randomly adsorbed phase III. DFT calculations show that SO42- binds via three oxygens to the bridge sites of the copper with sulfate being located directly above the copper vacancy in the (√3 × âˆš3)R30° adlayer, whereas the remaining oxygen of the sulfate points away from the surface. E-QCM measurement of the change of the electric charge due to Cu UPD Faradaic processes, the change of the interfacial mass due to the adsorption and desorption of Cu(II) and SO42-, and the formation and stripping of UPD copper on the gold surface provide complementary information that validates the EC-STM and DFT results. This work demonstrated the advantage of using complementary in situ experimental techniques (E-QCM and EC-STM) combined with simulations to obtain an accurate and complete picture of the dynamic interfacial adsorption and UPD processes at the electrode/electrolyte interface.

Cationic Tetrylene-Iron(0) Complexes: Access Points for Cooperative, Reversible Bond Activation and Open-Shell Iron(-I) Ferrato-Tetrylenes.

The open-shell cationic stannylene-iron(0) complex 4 (4=[PhiP DippSn⋅Fe⋅IPr]+ ; PhiP Dipp={[Ph2 PCH2 Si(i Pr)2 ](Dipp)N}; Dipp=2,6-i Pr2 C6 H3 ; IPr=[(Dipp)NC(H)]2 C:) cooperatively and reversibly cleaves dihydrogen at the Sn-Fe interface under mild conditions (1.5 bar, 298 K), in forming bridging hydrido-complex 6. The One-electron oreduction of the related GeII -Fe0 complex 3 leads to oxidative addition of one C-P linkage of the PhiP Dipp ligand in an intermediary Fe-I complex, leading to FeI phosphide species 7. One-electron reduction reaction of 4 gives access to the iron(-I) ferrato-stannylene, 8, giving evidence for the transient formation of such a species in the reduction of 3. The covalently bound tin(II)-iron(-I) compound 8 has been characterised through EPR spectroscopy, SQUID magnetometry, and supporting computational analysis, which strongly indicate a high localization of electron spin density at Fe-I in this unique d9 -iron complex.

Sensitivity of coupled cluster electronic properties on the reference determinant: Can Kohn-Sham orbitals be more beneficial than Hartree-Fock orbitals?

Coupled cluster calculations are traditionally performed over Hartree-Fock reference orbitals (HF-CC methodology). However, in the literature it has been repeatedly raised whether the use of a Kohn-Sham reference (KS-CC methodology) might result in improved performance relative to HF-CC. In the present study, we re-examine the relation of HF-CC and KS-CC methods by comparing the results of widely applied truncated CC calculations (CCSD, CCSD(T), CCSDT) to the limit of full configuration interaction (FCI), which serves as an undebatable reference point of accuracy. Based on a series of CC calculations on diatoms and transition metal complexes, we demonstrate that no systematic improvement of coupled cluster electronic energies, densities and chemical reaction energies is expected when changing from HF to a KS reference. Nevertheless, fortuitous error cancellations might occasionally result in illusory improvement compared to HF-CC. Altogether, the application of KS-CC is not advantageous over HF-CC, but it is also not unreasonable as the choice of reference has negligible influence on the results at sufficiently high CC levels. In addition, KS-CC can be a particularly useful alternative if difficulties are encountered in HF or HF-CC convergence. It is also notable that KS-CC results are found to be practically independent of the chosen density functional, which implies that almost any KS-CC method can be used in place of HF-CC.

Benchmarking Semiempirical QM Methods for Calculating the Dipole Moment of Organic Molecules.

The dipole moment is a simple descriptor of the charge distribution and polarity and is important for understanding and predicting various molecular properties. Semiempirical (SE) methods offer a cost-effective way to calculate dipole moment that can be used in high-throughput screening applications although the accuracy of the methods is still in question. Therefore, we have evaluated AM1, GFN0-xTB, GFN1-xTB, GFN2-xTB, PM3, PM6, PM7, B97-3c, HF-3c, and PBEh-3c SE methods, which cover a variety of SE approximations, to directly assess the performance of SE methods in predicting molecular dipole moments and their directions using 7211 organic molecules contained in the QM7b database. We find that B97-3c and PBEh-3c perform best against coupled-cluster reference values yielding dipole moments with a mean absolute error (MAE) of 0.10 and 0.11 D, respectively, which is similar to the MAE of density functional theory (DFT) methods (∼0.1 D) reported earlier. Analysis of the atomic composition shows that all SE methods show good performance for hydrocarbons for which the spread of error was within 1 D of the reference data, while the worst performances are for sulfur-containing compounds for which only B97-3c and PBEh-3c show acceptable performance. We also evaluate the effect of SE optimized geometry, instead of the benchmark DFT geometry, that shows a dramatic drop in the performance of AM1 and PM3 for which the range of error tripled. Based on our overall findings, we highlight that there is an optimal compromise between accuracy and computational cost using GFN2-xTB (MAE: 0.25 D) that is 3 orders of magnitude faster than B97-3c and PBEh-3c. Thus, we recommend using GFN2-xTB for cost-efficient calculation of the dipole moment of organic molecules containing C, H, O, and N atoms, whereas, for sulfur-containing organic molecules, we suggest PBEh-3c.

Toward Large-Scale Restricted Active Space Calculations Inspired by the Schmidt Decomposition.

We present an alternative, memory-efficient, Schmidt decomposition-based description of the inherently bipartite restricted active space (RAS) scheme, which can be implemented effortlessly within the density matrix renormalization group (DMRG) method via the dynamically extended active space procedure. Benchmark calculations are compared against state-of-the-art results of C2 and Cr2, which are notorious for their multireference character. Our results for ground and excited states together with spectroscopic constants demonstrate that the proposed novel approach, dubbed as DMRG-RAS, which is variational and free of uncontrolled method errors, has the potential to outperfom conventional methods for strongly correlated molecules.

Isolation and Reactivity of Tetrylene-Tetrylone-Iron Complexes Supported by Bis(N-Heterocyclic Imine) Ligands.

The germanium iron carbonyl complex 3 was prepared by the reaction of dimeric chloro(imino)germylene [IPrNGeCl]2 (IPrN=bis(2,6-diisopropylphenyl)imidazolin-2-iminato) with one equivalent of Collman's reagent (Na2 Fe(CO)4 ) at room temperature. Similarly, the reaction of chloro(imino)stannylene [IPrNSnCl]2 with Na2 Fe(CO)4 (1 equiv) resulted in the Fe(CO)4 -bridged bis(stannylene) complex 4. We observed reversible formation of bis(tetrylene) and tetrylene-tetrylone character in complexes 3 vs. 5 and 4 vs. 6, which was supported by DFT calculations. Moreover, the Li/Sn/Fe trimetallic complex 12 has been isolated from the reaction of [IPrNSnCl]2 with cyclopentadienyl iron dicarbonyl anion. The computational analysis further rationalizes the reduction pathway from these chlorotetrylenes to the corresponding complexes.

An Isolable Three-Coordinate Germanone and Its Reactivity.

A rare three-coordinate germanone [IPrN]2 Ge=O (IPrN=bis(2,6-diisopropylphenyl)imidazolin-2-imino) was successfully isolated. The germanone has a rather high thermal stability in arene solvent, and no detectable change was observed at 80 °C for at least one week. However, high thermal stability of [IPrN]2 Ge=O does not prevent its reactivity toward small molecules. Structural analysis and initial reactivity studies revealed the highly polarized nature of the terminal Ge=O bond. Besides, the addition of phenylacetylene, as well as O-atom transfer with 2,6-dimethylphenyl isocyanide make it a mimic of nucleophilic transition-metal oxides. Mechanism for O-atom transfer reaction was investigated via DFT calculations, which revealed that the reaction proceeds via a [2+2] cycloaddition intermediate.

Facile Access to Dative, Single, and Double Silicon-Metal Bonds Through M-Cl Insertion Reactions of Base-Stabilized SiII Cations.

Silicon(II) cations can offer fascinating reactivity patterns due to their unique electronic structure: a lone pair of electrons, two empty p orbitals and a positive charge combined on a single silicon center. We now report the facile insertion of N-heterocyclic carbene (NHC)-stabilized silyliumylidene ions into M-Cl bonds (M=Ru, Rh), forming a series of novel chlorosilylene transition-metal complexes. Theoretical investigations revealed a reaction mechanism in which the insertion into the M-Cl bond with concomitant 1,2-migration of a silicon-bound NHC to the transition metal takes place after formation of an initial silyliumylidene transition-metal complex. The mechanism could be verified experimentally through characterization of the intermediate complexes. Furthermore, the obtained chlorosilylene complexes can be conveniently utilized as synthons to access Si-M and Si=M bonding motifs bonds through reductive dehalogenation.

Distinguishing attosecond electron-electron scattering and screening in transition metals.

Electron-electron interactions are the fastest processes in materials, occurring on femtosecond to attosecond timescales, depending on the electronic band structure of the material and the excitation energy. Such interactions can play a dominant role in light-induced processes such as nano-enhanced plasmonics and catalysis, light harvesting, or phase transitions. However, to date it has not been possible to experimentally distinguish fundamental electron interactions such as scattering and screening. Here, we use sequences of attosecond pulses to directly measure electron-electron interactions in different bands of different materials with both simple and complex Fermi surfaces. By extracting the time delays associated with photoemission we show that the lifetime of photoelectrons from the d band of Cu are longer by ∼100 as compared with those from the same band of Ni. We attribute this to the enhanced electron-electron scattering in the unfilled d band of Ni. Using theoretical modeling, we can extract the contributions of electron-electron scattering and screening in different bands of different materials with both simple and complex Fermi surfaces. Our results also show that screening influences high-energy photoelectrons (≈20 eV) significantly less than low-energy photoelectrons. As a result, high-energy photoelectrons can serve as a direct probe of spin-dependent electron-electron scattering by neglecting screening. This can then be applied to quantifying the contribution of electron interactions and screening to low-energy excitations near the Fermi level. The information derived here provides valuable and unique information for a host of quantum materials.

Bis(silylene)-Stabilized Monovalent Nitrogen Complexes.

The first series of bis(silylene)-stabilized nitrogen(I) compounds is described. Starting from the 1,2-bis(N-heterocyclic silylenyl) 1,2-dicarba-closo-dedocaborane(12) scaffold 1, [1,2-(LSi)2 C2 B10 H10 ; L=PhC(Nt Bu)2 ], reaction with adamantyl azide (AdN3 ) affords the terminal N-µ2 -bridged zwitterionic carborane-1,2-bis(silylium) AdN3 adduct 2 with an open-cage dianionic nido-C2 B10 cluster core. Remarkably, upon one-electron reduction of 2 with C8 K and liberation of N2 and adamantane, the two silylene subunits are regenerated to furnish the isolable bis(silylene)-stabilized NI complex as an anion of 3 with the nido-C2 B10 cluster cage. On the other hand, one-electron oxidation of 2 with silver(I) yields the monocationic bis(silylene) NI complex 4 with the closo-C2 B10 cluster core. Moreover, the corresponding neutral NI radical complex 5 results from single-electron transfer from 3 to 4.

Versatile Tautomerization of EH2-Substituted Silylenes (E = N, P, As) in the Coordination Sphere of Nickel.

The synthesis and tautomerization of a "half-parent" aminosilylene and its heavy P- and As-analogues (TMSLSi-EH2; E = N, P, As; TMSL = N(SiMe3)(2,6- iPr2C6H3)) in the coordination sphere of nickel(0) to give the corresponding side-on η2-RSi(H)═EH and RH2Si-E ("silylpnictinidene") nickel complexes are reported. These complexes can be accessed through salt metathesis reactions of the lithium dihydropnictides LiEH2 with the acyclic chlorosilylene nickel(0) complex 1, [TMSL(Cl)Si → Ni(NHC)2; NHC = :C[( iPr)NC(Me)]2). In addition, we report the facile E-H bond activation reactions of EH3 with 1, which furnished a silyl nickel(II) complex through NH3 activation, but phosphido and arsenido complexes in the activation of PH3 and AsH3, respectively. Notably, reaction of 1 with LiNH2 leads to the acyclic bis(amido)silylene complex [TMSL(H2N)Si → Ni(NHC)2] 5, which does not undergo N-H proton migration to silicon(II) under ambient conditions. The transformation of the P- and As-analogues of 1 furnishes directly the respective side-on Si═E Ni complexes (nickelacycles), [η2-{TMSL(H)Si═E(H)}Ni(NHC)2] (E = P, 6; E = As, 9). These nickelacycles show a vastly different stability in solutions. While 6 is stable for several days at ambient temperature, 9 undergoes further rearrangement processes within minutes of its formation. Given the high acidity of the As-H proton in 9, however, this moiety can be trapped as a highly charge separated metalated-η2-silaarsene nickel complex 12 that is best described as an [AsSiNi] nickelacycle with Si-As multiple bond character. Taken as a whole, these results give, for the first time, insights into the relative stability of the tautomeric forms of side-on silaldimine transition metal complexes. The electronic nature and the rearrangement processes of these compounds were also investigated by quantum chemical calculations.

Heavier Carbonyl Olefination: The Sila-Wittig Reaction.

The Wittig reaction is one of the most versatile tools in the repertoire of organic chemists. Thus, a broad variety of carbonyl compounds can be converted to tailor-made alkenes with phosphorus ylides under mild conditions. However, no comparable reaction has been reported for silanones, the silicon congeners of ketones. Here, we demonstrate for the first time the successful application of the Wittig olefination to iminosilylsilanone 1. The selective formation of a series of silenes (R2Si═CR2) via the sila-Wittig reaction revealed an unprecedented approach to otherwise elusive compounds. In addition, the highly reactive and zwitterionic nature of 1 was also susceptible to nucleophilic attacks and cycloaddition reactions by and with the phosphorus ylides. Our results therefore make another important contribution to discovering the differences and similarities between carbon and silicon.

Amplification of Elementary Surface Reaction Steps on Transition Metal Surfaces Using Liquid Crystals: Dissociative Adsorption and Dehydrogenation.

Elementary reaction steps, including adsorption and dissociation, of a range of molecular adsorbates on transition metal surfaces have been elucidated in the context of chemical catalysis. Here we leverage this knowledge to design liquid crystals (LCs) supported on ultrathin polycrystalline gold films (predominant crystallographic face is (111)) that are triggered to undergo orientational transitions by dissociative adsorption and dehydrogenation reactions involving chlorine and carboxylic acids, respectively, thus amplifying these atomic-scale surface processes in situ into macroscopic optical signals. We use electronic structure calculations to predict that 4'-n-pentyl-4-biphenylcarbonitrile (5CB), a room temperature nematic LC, does not bind to Au(111) in an orientation that changes upon dissociative adsorption of molecular chlorine, a result validated by experiments. In contrast, 4-cyano-4-biphenylcarboxylic acid (CBCA) is calculated to bind strongly to Au(111) in a perpendicular orientation via dehydrogenation of the carboxylic acid group, which we confirmed using polarization-modulation infrared reflection-absorption spectroscopy. A maximum coverage of 0.07 monolayer of CBCA on the gold surface is sufficient to cause a perpendicular orientation of the LC. Dissociative adsorption of Cl2 gas on the gold surface, resulting in 0.5 monolayer coverage of Cl, displaces CBCA from Au(111) and thus triggers a strikingly visible change in orientation of the LC. Infrared spectroscopy established the orientation of adsorbed CBCA to be parallel to the Cl covered surface, with the COOH plane perpendicular to the surface, as predicted by first-principles calculations. These results demonstrate the use of first-principles calculations and transition metal surfaces to design LCs that report in situ targeted atomic-scale surface processes.

Isolation of an N-Heterocyclic Carbene Complex of a Borasilene.

Borasilenes, that is complexes which contain a boron-silicon double bond, have scarcely been isolated to date. In pursuit of such species, (Me3 Si)3 SiB(Cl)NHI (2, NHI=bulky N-heterocyclic imine) was prepared and treated with KOtBu to achieve formal extrusion of ClSiMe3 . The formation of an elusive borasilene (3int ) is postulated and it was verified by isolation of the N-heterocyclic carbene adduct (Me3 Si)2 SiB(I Me 4 )NHI (4, I Me 4 =1,3,4,5-tetramethyl-imidazolin-2-ylidene). X-ray crystallographic study and theoretical calculations on 4 diagnosed a boron-silicon double bond with marked zwitterionic character. The negative charge resides at the Si atom which marks the apex of a trigonal pyramid. Structural comparison of 4 with boron cation congeners (5+ , 6+ ) suggests that the positive charge is mainly located at the trigonal planar-coordinated B center. The conversion of 4 with pinacolborane (HBpin, 2 equiv) resulted in cleavage of the double bond to produce (Me3 Si)2 Si(Bpin)2 and (NHI)BH2 (I Me 4 ).

The Quest for Stable Silaaldehydes: Synthesis and Reactivity of a Masked Silacarbonyl.

The first donor-acceptor complex of a silaaldehyde, with the general formula (NHC)(Ar)Si(H)OGaCl3 (NHC=N-heterocyclic carbene), was synthesized using the reaction of silyliumylidene-NHC complex [(NHC)2 (Ar)Si]Cl with water in the presence of GaCl3 . Conversion of this complex to the corresponding silacarboxylate dimer [(NHC)(Ar)SiO2 GaCl2 ]2 , free silaacetal ArSi(H)(OR)2 , silaacyl chloride (NHC)(Ar)Si(Cl)OGaCl3 , and phosphasilene-NHC adduct (NHC)(Ar)Si(H)PTMS unveil its true potential as a synthon in silacarbonyl chemistry.

Exploring Hydrogen Evolution Accompanying Nitrogen Reduction on Biomimetic Nitrogenase Analogs: Can Fe-N xH yIntermediates Be Active Under Turnover Conditions?

Nitrogen reduction reaction (N2RR) carried out on biomimetic catalytic systems is considered to be a promising alternative for the traditional Haber-Bosch ammonia synthesis. Unfortunately, the selectivity of the currently known biomimetic catalysts is poor, as they also catalyze the unproductive hydrogen evolution reaction (HER). In the present computational study, we examine the HER activity of early N2RR intermediates in EP3 (E = B, Si) ligated single-site biomimetic iron complexes by calculating and comparing the activation Gibbs free energies of HER and N2RR elementary steps. We find that, in contrast to previous suggestions, early N2RR intermediates are not likely sources of HER under turnover conditions, as the barriers of the competing N2RR steps are significantly lower. Consequently, future research should focus on preventing other potential HER mechanisms, e.g., hydride formation, rather than accelerating the consumption of early N2RR intermediates as proposed earlier to design more efficient biomimetic catalysts.

Transition Metal Carbonyl Complexes of an N-Heterocyclic Carbene Stabilized Silyliumylidene Ion.

Silyliumylidene ions-Si(II) cations with a stereochemically active lone pair of electrons-can act as ligands in transition metal complexes comparable to silylenes. However, no investigations concerning their donor abilities have been carried out. Carbonyl complexes lend themselves exceptionally well to determine the donor/acceptor strength of various ligand systems. We now report the synthesis of novel group 6 and group 8 transition metal carbonyl complexes 2-5 of N-heterocyclic carbene (NHC) stabilized silyliumylidene ion 1b, including the first Cr, Mo, and Fe complexes of a Si(II) cation. The complexes were fully characterized by multinuclear NMR and IR spectroscopy and SC-XRD studies. A combination of experimentally determined IR bands together with theoretical calculations revealed weak σ-donor properties and a negligible π-acceptor ability of NHC-stabilized Si(II) cation 1b.

CO2 Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond.

CO2 fixation and reduction to value-added products is of utmost importance in the battle against rising CO2 levels in the Earth's atmosphere. An organoaluminum complex containing a formal aluminum double bond (dialumene), and thus an alkene equivalent, was used for the fixation and reduction of CO2 . The CO2 fixation complex undergoes further reactivity in either the absence or presence of additional CO2 , resulting in the first dialuminum carbonyl and carbonate complexes, respectively. Dialumene (1) can also be used in the catalytic reduction of CO2 , providing selective formation of a formic acid equivalent via the dialuminum carbonate complex rather than a conventional aluminum-hydride-based cycle. Not only are the CO2 reduction products of interest for C1 added value products, but the organoaluminum complexes isolated represent a significant step forward in the isolation of reactive intermediates proposed in many industrially relevant catalytic processes.

From As-Zincoarsasilene (LZn-As=SiL') to Arsaethynolato (As≡C-O) and Arsaketenylido (O=C=As) Zinc Complexes.

The reactivity of the As-zincosilaarsene LZn-As=SiL' A (L=[CH(CMeNDipp)2 ]- , Dipp=2,6-i Pr2 C6 H3 , L'=[{C(H)N(2,6-i Pr2 -C6 H3 )}2 ]2- ) towards small molecules was investigated. Due to the pronounced zwitterionic character of the Si=As bond of A, it undergoes addition reactions with H2 O and NH3 , forming LZnAs(H)SiOH(L') 1 and LZnAs(H)SiNH2 (L') 2. Oxygenation of A with N2 O at -60 °C furnishes the deep blue 1,2-disiloxydiarsene, [LZnOSi(L')As]2 4, presumably via dimerization of the arsinidene intermediate LZnOSi(L')As 3. Oxygenation of A with CO2 leads to the monomeric arsaethynolato siloxido zinc complex LZnOSi(L')(OC≡As) 5, essentially trapping the intermediary arsinidene 3 with liberated CO following initial oxidation of the Si=As bond. DFT calculations confirm the ambident coordination mode of the anionic [AsCO] ligand in solution, with the O-arsaethynolato [As≡C-O].- in 5, and the As-arsaketenylido ligand mode [O=C=As]- present in LZnO-Si(L')(-As=C=O) 5' akin to the analogous phosphorus system, [PCO]- .