Toward the Next Generation of Density Functionals: Escaping the Zero-Sum Game by Using the Exact-Exchange Energy Density.

ConspectusKohn-Sham density functional theory (KS DFT) is arguably the most widely applied electronic-structure method with tens of thousands of publications each year in a wide variety of fields. Its importance and usefulness can thus hardly be overstated. The central quantity that determines the accuracy of KS DFT calculations is the exchange-correlation functional. Its exact form is unknown, or better "unknowable", and therefore the derivation of ever more accurate yet efficiently applicable approximate functionals is the "holy grail" in the field. In this context, the simultaneous minimization of so-called delocalization errors and static correlation errors is the greatest challenge that needs to be overcome as we move toward more accurate yet computationally efficient methods. In many cases, an improvement on one of these two aspects (also often termed fractional-charge and fractional-spin errors, respectively) generates a deterioration in the other one. Here we report on recent notable progress in escaping this so-called "zero-sum-game" by constructing new functionals based on the exact-exchange energy density. In particular, local hybrid and range-separated local hybrid functionals are discussed that incorporate additional terms that deal with static correlation as well as with delocalization errors. Taking hints from other coordinate-space models of nondynamical and strong electron correlations (the B13 and KP16/B13 models), position-dependent functions that cover these aspects in real space have been devised and incorporated into the local-mixing functions determining the position-dependence of exact-exchange admixture of local hybrids as well as into the treatment of range separation in range-separated local hybrids. While initial functionals followed closely the B13 and KP16/B13 frameworks, meanwhile simpler real-space functions based on ratios of semilocal and exact-exchange energy densities have been found, providing a basis for relatively simple and numerically convenient functionals. Notably, the correction terms can either increase or decrease exact-exchange admixture locally in real space (and in interelectronic-distance space), leading even to regions with negative admixture in cases of particularly strong static correlations. Efficient implementations into a fast computer code (Turbomole) using seminumerical integration techniques make such local hybrid and range-separated local hybrid functionals promising new tools for complicated composite systems in many research areas, where simultaneously small delocalization errors and static correlation errors are crucial. First real-world application examples of the new functionals are provided, including stretched bonds, symmetry-breaking and hyperfine coupling in open-shell transition-metal complexes, as well as a reduction of static correlation errors in the computation of nuclear shieldings and magnetizabilities. The newest versions of range-separated local hybrids (e.g., ωLH23tdE) retain the excellent frontier-orbital energies and correct asymptotic exchange-correlation potential of the underlying ωLH22t functional while improving substantially on strong-correlation cases. The form of these functionals can be further linked to the performance of the recent impactful deep-neural-network "black-box" functional DM21, which itself may be viewed as a range-separated local hybrid.

Deuteration as a General Strategy to Enhance Azobenzene-Based Photopharmacology.

Chemical photoswitches have become a widely used approach for the remote control of biological functions with spatiotemporal precision. Several molecular scaffolds have been implemented to improve photoswitch characteristics, ranging from the nature of the photoswitch itself (e.g. azobenzenes, dithienylethenes, hemithioindigo) to fine-tuning of aromatic units and substituents. Herein, we present deuterated azobenzene photoswitches as a general means of enhancing the performance of photopharmacological molecules. Deuteration can improve azobenzene performance in terms of light sensitivity (higher molar extinction coefficient), photoswitch efficiency (higher photoisomerization quantum yield), and photoswitch kinetics (faster macroscopic rate of photoisomerization) with minimal alteration to the underlying structure of the photopharmacological ligand. We report synthesized deuterated azobenzene-based ligands for the optimized optical control of ion channel and G protein-coupled receptor (GPCR) function in live cells, setting the stage for the straightforward, widespread adoption of this approach.

Implementation and First Evaluation of Strong-Correlation-Corrected Local Hybrid Functionals for the Calculation of NMR Shieldings and Shifts.

Local hybrid functionals containing strong-correlation factors (scLHs) and range-separated local hybrids (RSLHs) have been integrated into an efficient coupled-perturbed Kohn-Sham implementation for the calculation of nuclear shielding constants. Several scLHs and the ωLH22t RSLH have then been evaluated for the first time for the extended NS372 benchmark set of main-group shieldings and shifts and the TM70 benchmark of 3d transition-metal shifts. The effects of the strong-correlation corrections have been analyzed with respect to the spatial distribution of the sc-factors, which locally diminish exact-exchange admixture at certain regions in a molecule. The scLH22t, scLH23t-mBR, and scLH23t-mBR-P functionals, which contain a "damped" strong-correlation factor to retain the excellent performance of the underlying LH20t functional for weakly correlated situations, tend to make smaller corrections to shieldings and shifts than the "undamped" scLH22ta functional. While the latter functional can also deteriorate agreement with the reference data in certain weakly correlated cases, it provides overall better performance, in particular for systems where static correlation is appreciable. This pertains only to a minority of systems in the NS372 main-group test set but to many more systems in the TM70 transition-metal test set, in particular for high-oxidation-state complexes, e.g., Cr(+VI) complexes and other systems with stretched bonds. Another undamped scLH, the simpler LDA-based scLH21ct-SVWN-m, also tends to provide significant improvements in many cases. The differences between the functionals and species can be rationalized on the basis of one-dimensional plots of the strong-correlation factors, augmented by isosurface plots of the fractional orbital density (FOD). Position-dependent exact-exchange admixture is thus shown to provide substantial flexibility in treating response properties like NMR shifts for both weakly and strongly correlated systems.

Revisiting Gauge-Independent Kinetic Energy Densities in Meta-GGAs and Local Hybrid Calculations of Magnetizabilities.

In a recent study [J. Chem. Theory Comput. 2021, 17, 1457-1468], some of us examined the accuracy of magnetizabilities calculated with density functionals representing the local density approximation (LDA), generalized gradient approximation (GGA), meta-GGA (mGGA), as well as global hybrid (GH) and range-separated (RS) hybrid functionals by assessment against accurate reference values obtained with coupled-cluster theory with singles, doubles, and perturbative triples [CCSD(T)]. Our study was later extended to local hybrid (LH) functionals by Holzer et al. [J. Chem. Theory Comput. 2021, 17, 2928-2947]; in this work, we examine a larger selection of LH functionals, also including range-separated LH (RSLH) functionals and strong-correlation LH (scLH) functionals. Holzer et al. also studied the importance of the physically correct handling of the magnetic gauge dependence of the kinetic energy density (τ) in mGGA calculations by comparing the Maximoff-Scuseria formulation of τ used in our aforementioned study to the more physical current-density extension derived by Dobson. In this work, we also revisit this comparison with a larger selection of mGGA functionals. We find that the newly tested LH, RSLH, and scLH functionals outperform all of the functionals considered in the previous studies. The various LH functionals afford the seven lowest mean absolute errors while also showing remarkably small standard deviations and mean errors. Most strikingly, the best two functionals are scLHs that also perform remarkably well in cases with significant multiconfigurational character, such as the ozone molecule, which is traditionally excluded from statistical error evaluations due to its large errors with common density functionals.

Unusually Large Effects of Charge-assisted C-H⋠⋠⋠F Hydrogen Bonds to Anionic Fluorine in Organic Solvents: Computational Study of 19 F NMR Shifts versus Thermochemistry.

A comparison of computed 19 F NMR chemical shifts and experiment provides evidence for large specific solvent effects for fluoride-type anions interacting with the σ*(C-H) orbitals in organic solvents like MeCN or CH2 Cl2 . We show this for systems ranging from the fluoride ion and the bifluoride ion [FHF]- to polyhalogen anions [ClFx ]- . Discrepancies between computed and experimental shifts when using continuum solvent models like COSMO or force-field-based descriptions like the 3D-RISM-SCF model show specific orbital interactions that require a quantum-mechanical treatment of the solvent molecules. This is confirmed by orbital analyses of the shielding constants, while less negatively charged fluorine atoms (e. g., in [EF4 ]- ) do not require such quantum-mechanical treatments to achieve reasonable accuracy. The larger 19 F solvent shift of fluoride in MeCN compared to water is due to the larger coordination number in the former. These observations are due to unusually strong charge-assisted C-H⋅⋅⋅F- hydrogen bonds, which manifest beyond some threshold negative natural charge on fluorine of ca. < -0.6 e. The interactions are accompanied by sizable free energies of solvation, in the order F- ≫[FHF]- >[ClF2 ]- >[ClF4 ]- . COSMO-RS solvation free energies tend to moderately underestimate those from the micro-solvated cluster treatment. Red-shifted and intense vibrational C-H stretching bands, potentially accessible in bulk solution, are further spectroscopic finger prints.

Systematic Evaluation of Modern Density Functional Methods for the Computation of NMR Shifts of 3d Transition-Metal Nuclei.

A wide range of density functionals from all rungs of Jacob's ladder have been evaluated systematically for a set of experimental 3d transition-metal NMR shifts of 70 complexes encompassing 12 × 49Ti, 10 × 51V, 10 × 53Cr, 11 × 55Mn, 9 × 57Fe, 9 × 59Co, and 9 × 61Ni shift values, as well as a diverse range of electronic structure characteristics. The overall 39 functionals evaluated include one LDA, eight GGAs, seven meta-GGAs (including their current-density-functional─CDFT─versions), nine global hybrids, four range-separated hybrids, eight local hybrids, and two double hybrids, and we also include Hartree-Fock and MP2 calculations. While recent evaluations of the same functionals for a very large coupled-cluster-based benchmark of main-group shieldings and shifts achieved in some cases aggregate percentage mean absolute errors clearly below 2%, the best results for the present 3d-nuclei set are in the range between 4 and 5%. Strikingly, the overall best-performing functionals are the recently implemented CDFT versions of two meta-GGAs, namely cM06-L (4.0%) and cVSXC (4.3%), followed by cLH14t-calPBE (4.9%), B3LYP (5.0%), and cLH07t-SVWN (5.1%), i.e., the previously best-performing global hybrid and two local hybrids. A number of further functionals achieve aggregate deviations in the range 5-6%. Range-separated hybrids offer no particular advantage over global hybrids. Due to the overall poor performance of Hartree-Fock theory for all systems except the titanium complexes, MP2 and double-hybrid functionals are unsuitable for these 3d-nucleus shifts and provide large errors. Global hybrid functionals with larger EXX admixtures, such as BHLYP or M06-2X, also perform poorly, and some other highly parametrized global hybrids also are unsuitable. For many functionals depending on local kinetic energy τ, their CDFT variants perform much better than their "non-CDFT" versions. This holds notably also for the above-mentioned M06-L and VSXC, while the effect is small for τ-dependent local hybrids and can even be somewhat detrimental to the agreement with experiment for a few other cases. The separation between well-performing and more poorly performing functionals is mainly determined by their results for the most critical nuclei 55Mn, 57Fe, and 59Co. Here either moderate exact-exchange admixtures or CDFT versions of meta-GGAs are beneficial for the accuracy. The overall deviations of the better-performing global or local hybrids are then typically dominated by the 53Cr shifts, where triplet instabilities appear to disfavor exact-exchange admixture. Further detailed analyses help to pinpoint specific nuclei and specific types of complexes that are challenges for a given functional.

Extended Benchmark Set of Main-Group Nuclear Shielding Constants and NMR Chemical Shifts and Its Use to Evaluate Modern DFT Methods.

An extended theoretical benchmark set, NS372, for light main-group nuclear shieldings and NMR shifts has been constructed based on high-level GIAO-CCSD(T)/pcSseg-3//CCSD(T)/cc-pVQZ reference data. After removal of the large static-correlation cases O3, F3-, and BH from the statistical evaluations for the 17O, 19F, and 11B subsets, the benchmark comprises overall 372 shielding values in 117 molecules with a wide range of electronic-structure situations, containing 124 1H, 14 11B, 93 13C, 43 15N, 31 17O, 47 19F, 14 31P, and 6 33S shielding constants. The CCSD(T)/pcSseg-3 data are shown to be close to the basis-set and method limit and thus provide an excellent benchmark to evaluate more approximate methods, such as density functional approaches. This dataset has been used to evaluate Hartree-Fock (HF) and MP2, and a wide range of exchange-correlation functionals from local density approximation (LDA) to generalized gradient approximations (GGAs) and meta-GGAs (focusing on their current-density functional implementations), as well as global hybrid, range-separated hybrid, local hybrid, and double-hybrid functionals. Starting with absolute shielding constants, the DSD-PBEP86 double hybrid is confirmed to provide the highest accuracy, with an aggregate relative mean absolute error (rel. MAE) of only 0.9%, followed by MP2 (1.1%). MP2 and double hybrids only show larger errors for a few systems with the largest static-correlation effects. The double-hybrid B2GP-PLYP, the two local hybrids cLH12ct-SsirPW92 and cLH12ct-SsifPW92, and the current-density functional meta-GGA cB97M-V follow closely behind (all 1.5%), as do some further functionals, cLH20t and cMN15-L (both 1.6%), as well as B2PLYP and KT3 (both 2.0%). Functionals on the lower rungs of the usual ladder offer the advantage of lower computational cost and access to larger molecules. Closer examination also reveals the best-performing methods for individual nuclei in the test set. Different ways of treating τ-dependent functionals are evaluated. When moving from absolute shielding constants to chemical shifts, some of the methods can benefit from systematic error compensation, and the overall error range somewhat narrows. Further methods now achieve the 2% threshold of relative MAEs, including functionals based on TPSS (TPSSh, cmPSTS).

Implementation and Validation of Local Hybrid Functionals with Calibrated Exchange-Energy Densities for Nuclear Shielding Constants.

A recently reported coupled-perturbed Kohn-Sham implementation to compute nuclear shielding constants with gauge-including atomic orbitals and local hybrid functionals has been extended to cover higher derivatives of the density in the local mixing function (LMF) of the local hybrid as well as the calibration function (CF) needed to deal with the ambiguity of exchange-energy densities. This allowed the first evaluation of state-of-the-art local hybrids with "calibrated" exchange-energy densities for nuclear shieldings. Compared to previously evaluated simpler local hybrids without a CF, appreciable improvements are found for proton shieldings. Furthermore, the recent LH20t functional is still competitive with the outstanding performance of the uncalibrated LH12ct-SsirSVWN and LH12ct-SsifSVWN LHs for heavier nuclei, suggesting that LH20t is possibly the most robust choice of any rung-four functional for computing the nuclear shieldings of main-group nuclei so far. Interestingly, the presence of a CF in the functional significantly reduces the number of artifacts introduced by the widely used Maximoff-Scuseria framework to treat the local kinetic energy τ. The latter occurs in so-called t-LMFs used in many of the present local hybrids. In any case, the use of Dobson's current-density functional framework is also recommended with more advanced calibrated τ-dependent local hybrid functionals.

Effect of the Current Dependence of Tau-Dependent Exchange-Correlation Functionals on Nuclear Shielding Calculations.

Exchange-correlation functionals that depend on the local kinetic energy τ are widely used in many fields. This includes meta-generalized gradient approximation (GGA) functionals and their global hybrid versions as well as local hybrid functionals with τ-dependent local mixing functions to determine position-dependent exact-exchange admixture. Under the influence of an external magnetic field, τ becomes dependent on the gauge of the magnetic vector potential and should thus be extended to a gauge-invariant formulation. The currently most widely used extension for nuclear shielding calculations is that suggested by Maximoff and Scuseria (Maximoff, S. N.; Scuseria, G. E. Chem. Phys. Lett. 2004, 390, 408). Using the recent first implementation of local hybrids in this framework, we have found unphysical paramagnetic contributions, which are most clearly identified for atoms but are also present in molecules. These τMS artifacts are small for the TPSS or TPSSh functionals, significantly deshielding in the case of nonhydrogen nuclei for the M06-L and M06 functionals and significantly shielding in those cases for the first-generation τ-dependent local hybrids LH07t-SVWN and LH12ct-SsifPW92. We have therefore implemented an extension of a linear-response nuclear shielding code to the proper current-density functional version of τ suggested by Dobson (Dobson, J. F. J. Chem. Phys. 1993, 98, 8870). Using τD eliminates the gauge dependence as well as the unphysical contributions introduced by τMS. A first evaluation of this implementation for a set of main-group nuclear shieldings against CCSD(T) benchmark data indicates rather small effects for the TPSS and TPSSh functionals but significant changes for the other functionals studied: the previously observed remarkable performance of the highly parameterized meta-GGA functional M06-L is found to be the result of error compensation with the lack of an explicit current dependence. Results for the M06 functional are improved somewhat but are still overall of relatively low accuracy. In contrast, too low proton shieldings found recently for τ-dependent local hybrids are improved significantly within the τD current-density functional framework while preserving the outstanding performance of these functionals for other nuclei.

Nuclear Spin-Spin Couplings: Efficient Evaluation of Exact Exchange and Extension to Local Hybrid Functionals.

We present an efficient implementation for the computation of nuclear spin-spin coupling tensors within density functional theory into the TURBOMOLE software suite. Emphasis is put on methods to efficiently evaluate the Hartree-Fock exchange needed for hybrid functionals: resolution of the identity and seminumerical evaluation on a grid. Our algorithm allows for the selection of specific nuclei for the reduction of calculation times. Further, the accuracy of locally dense basis sets in the density functional theory framework is investigated. These features allow for the routine computation of coupling constants in systems comprising about 100 carbon atoms within less than one day on a single CPU and within a few hours when using the OpenMP variant. Based on seminumerical integration, the first implementation of local hybrid functionals for spin-spin couplings is reported. This has allowed a preliminary evaluation of position-dependent exact-exchange admixture in three local hybrid functionals for a set of 80 isotropic spin-spin couplings in 23 small main-group molecules against CC3 and MCSCF reference data. Two of the local hybrids (LH14t-calPBE and LH07t-SVWN) are the top performers in the overall statistical evaluation compared to several standard functionals (TPSS, TPSSh, B3LYP, PBE0, and BHLYP), in particular, as they do not exhibit notable outliers for specific coupling types.

An Efficient Coupled-Perturbed Kohn-Sham Implementation of NMR Chemical Shift Computations with Local Hybrid Functionals and Gauge-Including Atomic Orbitals.

Nuclear shielding calculations for local hybrid (LH) functionals with position-dependent exact-exchange admixtures within a coupled-perturbed Kohn-Sham (CPKS) framework have been implemented into the Turbomole code using efficient seminumerical integration techniques to deal with two-electron integrals. When using gauge-including atomic orbitals, LHs generate additional terms within the "pre-loop" section of the CPKS scheme compared to global hybrid (GH) functionals, related to perturbed electron-repulsion integrals. These terms have been implemented and tested in detail, together with dependencies on grid sizes and integral screening procedures. Even with relatively small grids, a seminumerical treatment of GHs reproduces analytical GH results with high accuracy while improving scaling with system and basis-set sizes significantly. The extra terms generated by LHs in the pre-loop part increase the scaling of that contribution slightly, but the advantages compared to the analytical scheme are largely retained, in particular for the typically large basis sets used in NMR shift calculations, allowing for a very efficient computational scheme. An initial comparison of four first-generation LHs based on LDA exchange for a shielding test set of 15 small main-group molecules against high-level CCSD(T) benchmark data indicates a substantial reduction of the systematically underestimated shieldings compared to semilocal functionals or GHs for non-hydrogen nuclei when a so-called t-LMF is used to control the position dependence of the exact-exchange admixture. In contrast, proton shieldings are underestimated with this LMF, while an LH with a so-called s-LMF performs much better. These results are discussed in the context of experience for other properties, and they suggest directions for further improvements of LHs regarding nuclear shieldings.

Lessons from the Spin-Polarization/Spin-Contamination Dilemma of Transition-Metal Hyperfine Couplings for the Construction of Exchange-Correlation Functionals.

Hyperfine couplings (HFCs) of open-shell transition-metal centers are known to often depend crucially on core-shell spin polarization (CSSP). The latter is typically underestimated by semilocal density functionals, while admixture of exact exchange (EXX) in (global) hybrid functionals enhances CSSP. Unfortunately, a metal-ligand antibonding character of one or more of the singly occupied molecular orbitals of the complex will cause substantial valence-shell spin polarization (VSSP), which for global hybrids with higher EXX admixtures may lead to substantial spin contamination, thereby deteriorating the overall electronic structure and the dipolar couplings. In view of this known dilemma, we use a subset of 3d complexes from an earlier study (M. Munzarová, M. Kaupp J. Phys. Chem. A 1999, 103, 9966-9983) to examine systematically a wide range of exchange-correlation functionals for metal HFCs, including highly parametrized (meta-)GGAs, global, and range-separated hybrid functionals not yet available in earlier studies, as well as for the first time local hybrids with real-space position-dependent EXX admixture. Both CSSP and VSSP have been carefully analyzed in terms of their orbital contributions, both for cases dominated only by CSSP and for systems influenced crucially by VSSP and spin contamination. While some more parametrized meta-GGA functionals (τ-HCTH, VSXC, partially M06-L) provide surprisingly realistic CSSP, some others (MN12-L, MN15-L) and some global hybrids (M05, M06, partly MN15) exhibit dramatic shortcomings in describing the CSSP contributions. Local hybrid functionals provide a promising way of enhancing CSSP by high EXX admixture in the core region while avoiding excessive VSSP and thus spin contamination. These analyses provide important insights that may help to construct improved functionals for HFCs and related properties (e.g., contact NMR shifts).

A Computational Modeling Approach Predicts Interaction of the Antifungal Protein AFP from Aspergillus giganteus with Fungal Membranes via Its γ-Core Motif.

Fungal pathogens kill more people per year globally than malaria or tuberculosis and threaten international food security through crop destruction. New sophisticated strategies to inhibit fungal growth are thus urgently needed. Among the potential candidate molecules that strongly inhibit fungal spore germination are small cationic, cysteine-stabilized proteins of the AFP family secreted by a group of filamentous Ascomycetes. Its founding member, AFP from Aspergillus giganteus, is of particular interest since it selectively inhibits the growth of filamentous fungi without affecting the viability of mammalian, plant, or bacterial cells. AFPs are also characterized by their high efficacy and stability. Thus, AFP can serve as a lead compound for the development of novel antifungals. Notably, all members of the AFP family comprise a γ-core motif which is conserved in all antimicrobial proteins from pro- and eukaryotes and known to interfere with the integrity of cytoplasmic plasma membranes. In this study, we used classical molecular dynamics simulations combined with wet laboratory experiments and nuclear magnetic resonance (NMR) spectroscopy to characterize the structure and dynamical behavior of AFP isomers in solution and their interaction with fungal model membranes. We demonstrate that the γ-core motif of structurally conserved AFP is the key for its membrane interaction, thus verifying for the first time that the conserved γ-core motif of antimicrobial proteins is directly involved in protein-membrane interactions. Furthermore, molecular dynamic simulations suggested that AFP does not destroy the fungal membrane by pore formation but covers its surface in a well-defined manner, using a multistep mechanism to destroy the membranes integrity.IMPORTANCE Fungal pathogens pose a serious danger to human welfare since they kill more people per year than malaria or tuberculosis and are responsible for crop losses worldwide. The treatment of fungal infections is becoming more complicated as fungi develop resistances against commonly used fungicides. Therefore, discovery and development of novel antifungal agents are of utmost importance.

Reactivity of the Sterically Demanding Siloxanediol Mes2 Si(OH)(µ-O)Si(OH)Mes2 Towards Water and Ether Molecules.

A series of isotopologues of the siloxanediol Mes2 Si(OH)(µ-O)Si(OH)Mes2 (3 a) (Mes=2,4,6-trimethylphenyl) were synthesized by reactions of the corresponding disiloxane precursors Mes2 Si(µ-O)2 SiMes2 (2 a), Mes2 Si(µ-17 O)2 SiMes2 (2 b) or Mes2 Si(µ-18 O)2 SiMes2 (2 c) with an excess of H2 O, H217 O or H218 O. NMR and IR signal assignments for the siloxanediols in benzene are supported by quantum-chemical calculations, which indicate small energy differences between trans and cis conformers, the latter of which exhibits an intramolecular hydrogen bond. 1 H NMR as well as IR data suggest the presence of a mixture of both conformers in C6 D6 . Hydrogen-bonded adducts of Mes2 Si(OH)(µ-O)Si(OH)Mes2 with ethers such as diethylether, dimethoxyethane or dioxane were observed in the solid state, where they form polymeric chain-like structures. The latter appear to be stable only in the crystal. 17 O{1 H} NMR and IR data in THF solution suggest an interaction of 3 a with at least one THF molecule, whereas diethylether appears not to interact. Water adducts form neither in solution nor in the solid state as indicated by NMR and ATR IR data. 17 O{1 H} NMR and ESI-MS experiments illustrate the remarkably high stability of the siloxanediols towards water and show no evidence for intra- or intermolecular oxygen-exchange reactions. In marked contrast, a stepwise exchange of all three oxygen atoms-including the one in the Si-O-Si bridge-occurred in the gas phase, when [Mes2 Si(18 OH)(µ-18 O)Si(18 O)Mes2 ]- was treated with H2 O in the hexapole of an ESI FT-ICR mass spectrometer. The scrambling between the bridging and the other oxygen atoms likely proceeds through cyclic Si2 O2 intermediates.

Taming Silicon Congeners of CO and CO2 : Synthesis of Monomeric SiII and SiIV Chalcogenide Complexes.

The synthesis of the unprecedented monomeric SiII selenide complex (bis-NHC)Si=Se→GaCl3 2 (bis-NHC=bis-N heterocyclic carbene, H2 C[{NC(H)=C(H)N(Dipp)}C:]2 , Dipp=2,6-iPr2 C6 H3 ), bearing the elusive SiSe ligand as a heavy CO homologue by the reaction of the silylone-GaCl3 adduct (bis-NHC)Si→GaCl3 1 with elemental selenium in acetonitrile, is reported. The similar conversion of 1 with excess selenium conducted in THF afforded the SiSe2 complex (bis-NHC)Si(=Se)Se→GaCl3 3. Remarkably, the reaction of 1 with Te=P(nBu)3 as a gentle Te transfer reagent led to the isolation of the monomeric SiTe2 complex (bis-NHC)SiTe2 4, the first structurally characterized Lewis acid free heavy CO2 homologue complex. The isolated compounds 2, 3, and 4 have been fully characterized, including single-crystal X-ray diffraction analyses. Their electronic structures and spectroscopic data have also been studied by quantum-chemical calculations.

An Isolable Silicon Dicarbonate Complex from Carbon Dioxide Activation with a Silylone.

The first isolable molecular silicon dicarbonate complex (bis-NHC)Si(CO3 )2 2 (bis-NHC=H2 C[{NC(H)=C(H)N(Dipp)}C:]2 , Dipp=2,6-iPr2 C6 H3 ) was synthesized by facile reaction of the bis-N-heterocyclic carbene stabilized silylone (bis-NHC)Si 1, bearing a zero-valent silicon atom, with carbon dioxide. The monomeric silicon dioxide complex (bis-NHC)SiO2 3 supported by the bis-NHC ligand was proposed as a key intermediate resulting from double oxygenation of the zero-valent silicon atom in 1 by two molar equivalents of CO2 under liberation of CO; its subsequent Lewis acid-base reaction with CO2 leads to 2 which has been fully characterized including an single-crystal X-ray diffraction analysis. Its electronic structure, spectroscopic data and the thermochemistry of the formation have been studied quantum-chemically.