Mechanism of Nitrous Oxide Activation in C(sp2)-O Bond Formation Reactions Catalyzed by Nickel Complexes.

Recent groundbreaking experimental reports demonstrated that Ni complexes bearing a bidentate- or tridentate-bipyridine-based ligand can be used to activate N2O for use as an O-transfer agent in C(sp2)-O bond formation reactions under mild experimental conditions. In this work, quantum chemical calculations are used to shed light on the mechanism through which such metal complexes catalytically activate nitrous oxide, providing new fundamental insights into the development of novel catalysts for N2O revalorization. As a case study, we consider the recent work by Cornella and co-workers (Nature, 2022, 604, 677) concerning the synthesis of phenols from aryl halides at room temperature, which requires the use of an external reducing agent. Our results suggest that the metal center remains in its Ni(II) oxidation state throughout the whole catalytic cycle, despite the presence of various redox steps in the mechanism and the Ni ability to maneuver between a number of oxidation states. This counterintuitive behavior is made possible by the ligand redox activity in the catalytic process, which involves accepting electrons from the reducing agent. Several possible pathways are systematically investigated, each associated with distinct activation modes, kinetics, and reaction outcomes. The governing factors in dictating the preferred path lie in the electronic nature of the ligand (strong vs weak field) and its geometric structure (specifically, the number of coordinating arms). These characteristics play a pivotal role in determining whether the process follows a catalytic or stoichiometric route and can be in principle modulated for the design of new metal complexes with tailored redox properties and reactivity.

Monomeric gold hydrides for carbon dioxide reduction: ligand effect on the reactivity.

We analyzed the ligand electronic effect in the reaction between a [LAu(I)H]0/- hydride species and CO2, leading to a coordinated formate [LAu(HCOO)]0/-. We explored 20 different ligands, such as carbenes, phosphines and others, carefully selected to cover a wide range of electron-donor and -acceptor properties. We included in the study the only ligand, an NHC-coordinated diphosphene, that, thus far, experimentally demonstrated facile and reversible reaction between the monomeric gold(I) hydride and carbon dioxide. We elucidated the previously unknown reaction mechanism, which resulted to be concerted and common to all the ligands: the gold-hydrogen bond attacks the carbon atom of CO2 with one oxygen atom coordinating to the gold center. A correlation between the ligand σ donor ability, which affects the electron density at the reactive site, and the kinetic activation barriers of the reaction has been found. This systematic study offers useful guidelines for the rational design of new ligands for this reaction, while suggesting a few promising and experimentally accessible potential candidates for the stoichiometric or catalytic CO2 activation.

The Chemical Bond at the Bottom of the Periodic Table: The Case of the Heavy Astatine and the Super-Heavy Tennessine.

In this work, we study the chemical bond in molecules containing heavy and super-heavy elements according to the current state-of-the-art bonding models. An Energy Decomposition Analysis in combination with Natural Orbital for Chemical Valence (EDA-NOCV) within the relativistic four-component Dirac-Kohn-Sham (DKS) framework is employed, which allows to successfully include the spin-orbit coupling (SOC) effects on the chemical bond description. Simple halogen-bonded adducts ClX⋯L (X=At, Ts; L=NH3, Br-, H2O, CO) of astatine and tennessine have been selected to assess a trend on descending along a group, while modulating the ClX⋯L bond features through the different electronic nature of the ligand L. Interesting effects caused by SOC have been revealed: i) a huge increase of the ClTs dipole moment (which is almost twice as that of ClAt), ii) a lowering of the ClX⋯L bonding energy arising from different contributions to the ClX…L interaction energy strongly depending on the nature of L, iii) a quenching of one of the π back-donation components to the bond. In the ClTs(CO) adduct, the back-donation from ClTs to CO becomes the most important component. The analysis of the electronic structure of the ClX dimers allows for a clear interpretation of the SOC effects in these systems.

Organocatalytic DYKAT of Si-Stereogenic Silanes.

Chiral organosilanes do not exist in nature and are therefore absent from the "chiral pool". As a consequence, synthetic approaches toward enantiopure silanes, stereogenic at silicon, are rather limited. While catalytic asymmetric desymmetrization reactions of symmetric organosilicon compounds have been developed, the utilization of racemic silanes in a dynamic kinetic asymmetric transformation (DYKAT) or dynamic kinetic resolution (DKR) would significantly expand the breadth of accessible Si-stereogenic compounds. We now report a DYKAT of racemic allyl silanes enabled by strong and confined imidodiphosphorimidate (IDPi) catalysts, providing access to Si-stereogenic silyl ethers. The products of this reaction are easily converted into useful enantiopure monohydrosilanes. We propose a spectroscopically and experimentally supported mechanism involving the epimerization of a catalyst-bound intermediate.

Widening the Landscape of Small Molecule Activation with Gold-Aluminyl Complexes: A Systematic Study of E-H (E=O, N) Bonds, SO2 and N2 O Activation.

The electronic features of gold-aluminyl complexes have been thoroughly explored. Their similarity with Group 14 dimetallenes and other metal-aluminyl complexes suggests that their reactivity with small molecules beyond carbon dioxide could be accessed. In this work, the reactivity of the [t Bu3 PAuAl(NON)] (NON=4,5-bis(2,6 diisopropylanilido)-2,7-ditert-butyl-9,9-dimethylxanthene) complex towards water, ammonia, sulfur dioxide and nitrous oxide is computationally explored. The reaction mechanisms computed for each substrate strongly suggest that all activation processes are in principle experimentally feasible. Electronic structure analysis highlights that, in all cases, the reactivity is driven by the presence of the poorly polarized electron-sharing gold-aluminyl bond, which induces a radical-like reactivity of the complex towards all the substrates. A flat topology of the potential energy surface (PES) has been found for the reaction with N2 O, where two almost isoenergetic transition states can be located along the same reaction coordinate with different geometries, suggesting that the N2 O binding mode may not be a good indicator of the nature of N2 O activation in a cooperative bimetallic reactivity. In addition, the catalytic potentialities of these complexes have been explored in the framework of nitrous oxide reduction. The study reveals that the [t Bu3 PAuAl(NON)] complex might be an efficient catalyst towards oxidation of phosphines (and boranes) via N2 O reduction. These findings underline recurring trends in the novel chemistry of gold-aluminyl complexes and call for experimental feedbacks.

An ETS-NOCV-based computational strategies for the characterization of concerted transition states involving CO2.

Due to the presence of both a slightly acidic carbon and a slightly basic oxygen, carbon dioxide is often involved in concerted transition states (TSs) with two (or more) different molecular events interlaced in the same step. The possibility of isolating and quantitatively evaluating each molecular event would be important to characterize and understand the reaction mechanism in depth. This could be done, in principle, by measuring the relevant distances in the optimized TS, but often distances are not accurate enough, especially in the presence of many simultaneous processes. Here, we have applied the Extended Transition State-Natural Orbital for Chemical Valence-method (ETS-NOCV), also in combination with the Activation Strain Model (ASM) and Energy Decomposition Analysis (EDA), to separate and quantify these molecular events at the TS of both organometallic and organic reactions. For the former, we chose the decomposition of formic acid to CO2 by an iridium catalyst, and for the latter, a CO2 -mediated transamidation and its chemical variations (hydro- and aminolysis of an ester) as case studies. We demonstrate that the one-to-one mapping between the "molecular events" and the ETS-NOCV components is maintained along the entire lowest energy path connecting reactants and products around the TS, thus enabling a detailed picture on the relative importance of each interacting component. The methodology proposed here provides valuable insights into the effect of different chemical substituents on the reaction mechanism and promises to be generally applicable for any concerted TSs.

What Singles out Aluminyl Anions? A Comparative Computational Study of the Carbon Dioxide Insertion Reaction in Gold-Aluminyl, -Gallyl, and -Indyl Complexes.

Anionic aluminum(I) anions ("aluminyls") are the most recent discovery along Group 13 anions, and the understanding of the unconventional reactivity they are able to induce at a coordinated metal site is at an early stage. A striking example is the efficient insertion of carbon dioxide into the Au-Al bond of a gold-aluminyl complex. The reaction occurs via a cooperative mechanism, with the gold-aluminum bond being the actual nucleophile and the Al site also behaving as an electrophile. In the complex, the Au-Al bond has been shown to be mainly of an electron-sharing nature, with the two metal fragments displaying a diradical-like reactivity with CO2. In this work, the analogous reactivity with isostructural Au-X complexes (X = Al, Ga, and In) is computationally explored. We demonstrate that a kinetically and thermodynamically favorable reactivity with CO2 may only be expected for the gold-aluminyl complex. The Au-Al bond nature, which features the most (nonpolar) electron-sharing character among the Group 13 anions analyzed here, is responsible for its highest efficiency. The radical-like reactivity appears to be a key ingredient to stabilize the CO2 insertion product. This investigation elucidates the special role of Al in these hetero-binuclear compounds, providing new insights into the peculiar electronic structure of aluminyls, which may help for the rational control of their unprecedented reactivity toward carbon dioxide.

Mechanistic Study of Alkyne Insertion into Cu-Al and Au-Al Bonds: A Paradigm Shift for Coinage Metal Chemistry.

In this work, the mechanism of the insertion reaction of 3-hexyne into Cu-Al and Au-Al bonds in M-aluminyl (M = Cu, Au) complexes is computationally elucidated. The mechanism is found to be radical-like, with the Cu-Al and Au-Al bonds acting as nucleophiles toward the alkyne, and predicts a less efficient reactivity for the gold-aluminyl complex. The proposed mechanism well rationalizes the kinetic (or thermodynamic) control on the formation of the syn (or anti) insertion product into the Cu-Al bond (i.e., dimetallated alkene) which has been recently reported. A comparative analysis of the electronic structure reveals that the reduced reactivity at the gold site─usually showing higher efficiency than copper as a "standard" electrophile in alkyne activation─arises from a common feature, i.e., the highly stable 6s Au orbital. The relativistic lowering of the 6s orbital, making it more suitable for accepting electron density and thus enhancing the electrophilicity of gold complexes, in the gold-aluminyl system is responsible for a less nucleophilic Au-Al bond and, consequently, a less efficient alkyne insertion. These findings demonstrate that the unconventional electronic structure and the electron-sharing nature of the M-Al bond induce a paradigm shift in the properties of coinage metal complexes. In particular, the peculiar radical-like reactivity, previously shown also with carbon dioxide, suggests that these complexes might efficiently insert/activate other small molecules, opening new and unexplored paths for their reactivity.

Gold-Aluminyl and Gold-Diarylboryl Complexes: Bonding and Reactivity with Carbon Dioxide.

The unconventional carbon dioxide insertion reaction of a gold-aluminyl [tBu3PAuAl(NON)] complex has been recently shown to be related to the electron-sharing character of the Au-Al bond that acts as a nucleophile and stabilizes the insertion product through a radical-like behavior. Since a gold-diarylboryl [IPrAuB(o-tol)2] complex with similar reactivity features has been recently reported, in this work we computationally investigate the reaction of carbon dioxide with [LAuX] (L = phosphine, N-heterocyclic carbene (NHC); X = Al(NON), B(o-tol)2) complexes to get insights into the Al/B anionic and gold ancillary ligand effects on the Au-Al/B bond nature, electronic structure, and reactivity of these compounds. We demonstrate that the Au-Al and Au-B bonds possess a similar electron-sharing nature, with diarylboryl complexes displaying a slightly more polarized bond as Au(δ+)-B(δ-). This feature reduces the radical-like reactivity toward CO2, and the Al/B anionic ligand effect is found to favor aluminyls over boryls, despite the greater oxophilicity of B. Remarkably, the ancillary ligand of gold has a negligible electronic trans effect on the Au-X bond and only a minor impact on the formation of the insertion product, which is slightly more stable with carbene ligands. Surprisingly, we find that the modification of the steric hindrance at the carbene site may exert a sizable control over the reaction, with more sterically hindered ligands thermodynamically disfavoring the formation of the CO2 insertion product.

Reactivity of a Gold-Aluminyl Complex with Carbon Dioxide: A Nucleophilic Gold?

A gold-aluminyl complex has been recently reported to feature an unconventional gold nucleophilic center, which was revealed through reactivity with carbon dioxide leading to the Au-CO2 coordination mode. In this work, we computationally investigate the reaction mechanism, which is found to be cooperative, with the gold-aluminum bond being the actual nucleophile and Al also behaving as electrophile. The Au-Al bond is shown to be mainly of an electron-sharing nature, with the two metal fragments displaying a diradical-like reactivity with CO2.

Understanding the Deactivation Pathways of Iridium(III) Pyridine-Carboxiamide Catalysts for Formic Acid Dehydrogenation.

The degradation pathways of highly active [Cp*Ir(κ2 -N,N-R-pica)Cl] catalysts (pica=picolinamidate; 1 R=H, 2 R=Me) for formic acid (FA) dehydrogenation were investigated by NMR spectroscopy and DFT calculations. Under acidic conditions (1 equiv. of HNO3 ), 2 undergoes partial protonation of the amide moiety, inducing rapid κ2 -N,N to κ2 -N,O ligand isomerization. Consistently, DFT modeling on the simpler complex 1 showed that the κ2 -N,N key intermediate of FA dehydrogenation (INH ), bearing a N-protonated pica, can easily transform into the κ2 -N,O analogue (INH2 ; ΔG≠ ≈11 kcal mol-1 , ΔG ≈-5 kcal mol-1 ). Intramolecular hydrogen liberation from INH2 is predicted to be rather prohibitive (ΔG≠ ≈26 kcal mol-1 , ΔG≈23 kcal mol-1 ), indicating that FA dehydrogenation should involve mostly κ2 -N,N intermediates, at least at relatively high pH. Under FA dehydrogenation conditions, 2 was progressively consumed, and the vast majority of the Ir centers (58 %) were eventually found in the form of Cp*-complexes with a pyridine-amine ligand. This likely derived from hydrogenation of the pyridine-carboxiamide via a hemiaminal intermediate, which could also be detected. Clear evidence for ligand hydrogenation being the main degradation pathway also for 1 was obtained, as further confirmed by spectroscopic and catalytic tests on the independently synthesized degradation product 1 c. DFT calculations confirmed that this side reaction is kinetically and thermodynamically accessible.

Efficient Computation of Geometries for Gold Complexes.

Computationally obtaining structural parameters along a reaction coordinate is commonly performed with Kohn-Sham density functional theory which generally provides a good balance between speed and accuracy. However, CPU times still range from inconvenient to prohibitive, depending on the size of the system under study. Herein, the tight binding GFN2-xTB method [C. Bannwarth, S. Ehlert, S. Grimme, J. Chem. Theory Comput. 2019, 15, 1652] is investigated as an alternative to produce reasonable geometries along a reaction path, that is, reactant, product and transition state structures for a series of transformations involving gold complexes. A small mean error (1 kcal/mol) was found, with respect to an efficient composite hybrid-GGA exchange-correlation functional (PBEh-3c) paired with a double-ζ basis set, which is 2-3 orders of magnitude slower. The outlined protocol may serve as a rapid tool to probe the viability of proposed mechanistic pathways in the field of gold catalysis.

Monitoring of the Pre-Equilibrium Step in the Alkyne Hydration Reaction Catalyzed by Au(III) Complexes: A Computational Study Based on Experimental Evidences.

The coordination ability of the [(ppy)Au(IPr)]2+ fragment [ppy = 2-phenylpyridine, IPr = 1,3-bis(2,6-di-isopropylphenyl)-imidazol-2-ylidene] towards different anionic and neutral X ligands (X = Cl-, BF4-, OTf-, H2O, 2-butyne, 3-hexyne) commonly involved in the crucial pre-equilibrium step of the alkyne hydration reaction is computationally investigated to shed light on unexpected experimental observations on its catalytic activity. Experiment reveals that BF4- and OTf- have very similar coordination ability towards [(ppy)Au(IPr)]2+ and slightly less than water, whereas the alkyne complex could not be observed in solution at least at the NMR sensitivity. Due to the steric hindrance/dispersion interaction balance between X and IPr, the [(ppy)Au(IPr)]2+ fragment is computationally found to be much less selective than a model [(ppy)Au(NHC)]2+ (NHC = 1,3-dimethylimidazol-2-ylidene) fragment towards the different ligands, in particular OTf- and BF4-, in agreement with experiment. Effect of the ancillary ligand substitution demonstrates that the coordination ability of Au(III) is quantitatively strongly affected by the nature of the ligands (even more than the net charge of the complex) and that all the investigated gold fragments coordinate to alkynes more strongly than H2O. Remarkably, a stabilization of the water-coordinating species with respect to the alkyne-coordinating one can only be achieved within a microsolvation model, which reconciles theory with experiment. All the results reported here suggest that both the Au(III) fragment coordination ability and its proper computational modelling in the experimental conditions are fundamental issues for the design of efficient catalysts.

Spin-Forbidden Reactivity of Transition Metal Oxo Species: Exploring the Potential Energy Surfaces.

Spin-forbidden reactions are frequently encountered when transition metal oxo species are involved, particularly in oxygen transfer reactivity. The computational study of such reactions is challenging, because reactants and products are located on different spin potential energy surfaces (PESs). One possible approach to describe these reactions is the so-called minimum energy crossing point (MECP) between the diabatic reactants and products PESs. Alternatively, inclusion of spin-orbit coupling (SOC) effects allows to locate a saddle point on a single adiabatic PES (TS SOC). The TS SOC approach is rarely applied because of its high computational cost. Recently evidence for a TS SOC impact on significantly lowering the activation barrier in dioxygen addition to a carbene-gold(I)-hydride complex reaction (Chem. Sci. 2016, 7, 7034-7039) or even on predicting a qualitatively different reaction mechanism in mercury methylation by cobalt corrinoid (Angew. Chem. Int. Ed. 2016, 55, 11503-11506) has been put forward. Using MECP and TS SOC approaches a systematic analysis is provided here of three prototypical transition metal oxo spin-forbidden processes to investigate their implications on reactivity. Cycloaddition of ethylene to chromyl chloride (CrO2 Cl2 +C2 H4 ), iron oxide cation insertion into the hydrogen molecule (FeO+ +H2 ) and H-abstraction from toluene by a MnV -oxo-porphyrin cation (MnOP(H2 O)+ +C6 H5 CH3 ) are case studies. For all these processes the MECP and TS SOC results are compared, which show that the spin-forbidden reactivity of transition metal oxo species can be safely described by a MECP approach, at least for the first-row transition metals investigated here, where the spin-orbit coupling is relatively weak. However, for the Mn-oxo reactivity, the MECP and TS SOC have been found to be crucial for a correct description of the reaction mechanism. In particular, the TS SOC approach allows to straightforwardly explore detailed features of the adiabatic potential energy surface which in principle could affect the overall reaction rate in cases where the involved diabatic PESs are tricky.

Ground and excited electronic states of AuH2via detachment energies on AuH2- using state-of-the-art relativistic calculations.

Photoelectron spectroscopy (PES) is a well-known technique which provides unique information about the electronic structure of anionic and neutral species of simple molecules containing heavy elements; however, the detailed interpretation of the resulting experimental spectra can be very complex and theoretical support is mandatory. In this work, based on the available vibrationally resolved PES experiments for gold dihydride (Liu, H.-T. et al., Chem. Sci., 2012, 3, 3286), we have employed several relativistic theoretical approaches with the aim of reproducing experimental photoelectron Detachment Energies (DEs) of AuH2- to give a neutral open-shell molecule, AuH2. The results are discussed in terms of relativistic effects, orbital relaxation and electron correlation. In order to reproduce accurate DEs it has been necessary to include all these effects in a consistent manner at a high degree of accuracy, by means of the equation-of-motion coupled-cluster theory (EOM-IP-CCSD) based on the relativistic exact two-component Hamiltonian (Shee A. et al. J. Chem. Phys., 2018, 174113). This method has also been applied for investigating the ground and low-lying electronic potential energy surfaces of the neutral open shell AuH2 species. The equilibrium geometry of the AuH2 ground state is found to be bent, which is fully consistent with the experimental findings, while all the excited states, including the first, which was previously suggested to have a slightly bent structure, are found to be linear. In the linear centrosymmetric nuclear configuration (which corresponds to the equilibrium geometry of the anion, AuH2-), we find that the first excited state and ground state are very close in energy and the ground state is characterized by an unexpected symmetry breaking in the direction of the asymmetric stretching, due to the pseudo-Jahn-Teller effect. This effect depends on the energy difference between these two electronic states and disappears when the spin-orbit coupling is neglected. The picture that emerges here is intriguing and demonstrates that the interpretation, for which the vibronic transitions that were previously assigned to a slightly bent structure of the first excited state needs to be revised and that a full rationalization of the PES spectra would require the explicit inclusion of the nuclear dynamical effects, beyond the Born-Oppenheimer (BO) approximation. From a methodological point of view, the relativistic EOM-IP-CCSD method results are highly accurate and capable of giving a well-balanced description of the anionic and neutral species, which is a key aspect for the interpretation of the PES spectra in open-shell heavy element compounds.

Spin-orbit coupling is the key to unraveling intriguing features of the halogen bond involving astatine.

The effect of spin-orbit coupling (SOC) on the halogen bond involving astatine has been investigated using state-of-the-art two- and four-component relativistic calculations. Adducts between Cl-X (X = Cl, Br, I and At) and ammonia have been selected to establish a trend on going down the periodic table. The SOC influence has been explored not only on the geometric and energetic features that can be used to characterize the halogen bond strength but also on the three main contributions to it that are the charge transfer, the "σ-hole" (i.e. the localized region with a net positive electrostatic potential at the halogen site) and the "polar flattening" (which is related to the effective shape of the halogen site). A surprisingly large increase of the Cl-At dipole moment, due to the inclusion of SOC, has been worked out using four-component CCSD(T) reference calculations, indicating that this bond is significantly more ionic than one may predict. Due to the SOC effect, which induces a peculiar charge accumulation on the At side in the Cl-At dimer, a weakening of the astatine-mediated halogen bond occurs arising from the (i) reduced amount of charge transfer, (ii) decrease of the polar flattening and (iii) lowering of the short-range Coulomb potential. The analysis of the electronic structure of the Cl-At moiety allows for a rationalization of the SOC effects on all the considered features of the halogen bond, including an unprecedented unsymmetrical charge back-donation from Cl-At to ammonia.

Spectroscopic/Bond Property Relationship in Group 11 Dihydrides via Relativistic Four-Component Methods.

Group 11 dihydrides MH2- (M = Cu, Ag, Au, Rg) have been much less studied than the corresponding MH compounds, despite having potentially several interesting applications in chemical research. In this work, their main spectroscopic constants (bond lengths, dissociation energies, and force constants) have been evaluated by means of highly accurate relativistic four-component coupled cluster (4c-CCSD(T)) calculations in combination with large basis sets. Periodic trends have been quantitatively explained by the charge-displacement/natural orbitals for chemical valence (CD-NOCV) analysis based on the four-component relativistic Dirac-Kohn-Sham method, which allows a consistent picture of the nature of the M-H bond to be obtained on going down the periodic table in terms of Dewar-Chatt-Duncanson bonding components. A strong ligand-to-metal donation drives the M-H bond and it is responsible for the heterolytic (HM···H-) dissociation energies to increase monotonically from Cu to Rg, with RgH2- showing the strongest and most covalent M-H bond. The "V"-shaped trend observed for the bond lengths, dissociation energies, and stretching frequencies can be explained in terms of relativistic effects and, in particular, of the relativistically enhanced sd hybridization occurring at the metal, which affects the metal-ligand distances in heavy transition-metal complexes. The sd hybridization is very small for Cu and Ag, whereas it becomes increasingly important for Au and Rg, being responsible for the increasing covalent character of the bond, the sizable contraction of the Au-H and Rg-H bonds, and the observed trend. This work rationalizes the spectroscopic/bond property relationship in group 11 dihydrides within highly accurate relativistic quantum chemistry methods, paving the way for their applications in chemical bond investigations involving heavy and superheavy elements.

Cationic Gold(I) Diarylallenylidene Complexes: Bonding Features and Ligand Effects.

Using computational approaches, we qualitatively and quantitatively assess the bonding components of a series of experimentally characterized Au(I) diarylallenylidene complexes (N.Kim, R.A.Widenhoefer, Angew. Chem. Int. Ed. 2018, 57, 4722-4726). Our results clearly demonstrate that Au(I) engages only weakly in π-backbonding, which is, however, a tunable bonding component. Computationally identified trends in bonding are clearly correlated with the substitution patterns of the aryl substituents in the Au(I) diarylallenylidene complexes and good agreement is found with the previously reported experimental data, such as IR spectra, 13 C NMR chemical shifts and rates of decomposition together with their corresponding barrier heights, further substantiating the computational findings. The description of the bonding patterns in these complexes allow predictions of their spectroscopic features, their reactivity and stability.

Alkyne Activation with Gold(III) Complexes: A Quantitative Assessment of the Ligand Effect by Charge-Displacement Analysis.

A quantitative assessment of the Dewar-Chatt-Duncanson components of the Au(III)-alkyne bond in a series of cationic and dicationic bis- and monocyclometalated gold(III) complexes with 2-butyne via charge-displacement (CD) analysis is reported. Bonding between Au(III) and 2-butyne invariably shows a dominant σ donation component, a smaller, but significant, π back-donation, and a remarkable polarization of the alkyne CC triple bond toward the metal fragment. A very large net electron charge transfer from CC triple bond to the metal fragment results, which turns out to be unexpectedly insensitive to the charge of the complex and more strictly related to the nature of the ancillary ligand. The combination of σ donation, π back-donation, and polarization effects is in fact modulated by the different ligand frameworks, with ligands bearing atoms different from carbon in trans position with respect to the alkyne emerging as especially interesting for both imparting Au(III)-alkyne bond stability and inducing a more effective alkyne activation. A first attempt to figure out a rationale on the bonding/reactivity relationship for Au(III)-alkyne is made by performing a comparative study in a model nucleophilic attack of water to the alkyne triple bond. Smaller π back-donation facilitates alkyne slippage in the transition states, which is energetically less demanding for Au(III) than for Au(I), and suggests a greater propensity of Au(III) to facilitate the nucleophilic attack.

Understanding the Reactivity of Mn-Oxo Porphyrins for Substrate Hydroxylation: Theoretical Predictions and Experimental Evidence Reconciled.

The Mn-oxo porphyrin (MnOP) mechanism for substrate hydroxylation is computationally studied with the aim to better understand reactivity in these systems. Theoretical studies suggest Mn(V)OP species to be very reactive intermediates with thermally accessible reaction barriers represented by low-spin/high-spin-crossover occurring in the Mn(V)OP oxidant, and kinetics for selected Mn(V)OP species indeed find high reactivity. On the other hand, MnOP complexes lead to modest yields in hydroxylation reactions of several different substrates, implying low rate constants and high reaction barriers. The resolution of this inconsistency is very important to understand the reactivity of Mn-oxo porphyrins and to improve the catalytic conditions. In this work we use the toluene hydroxylation by the Mn(V)OP(H2O)+ complex as a case study to gain deep insight into the reaction mechanism. Minimum energy crossing point (MECP) results on the H-abstraction process from toluene indicate a first crossover from a singlet to a triplet spin state of the Mn(V)OP(H2O)+ species with a thermally accessible barrier, followed by a very facile H-abstraction by the triplet complex. Issues concerning (i) the validation of the level of the density functional theory employed (BP86) to describe the singlet-triplet energy gap in the Mn(V)OP(H2O)+ system versus highly accurate DMRG-CASPT2/CC calculations, and (ii) the influence of the axial ligand (X = none, Cl-, CH3CN, OH-, and O2-) on MnOP reactivity, which models the different experimental conditions, are addressed. The ligand trans influence mainly controls the reactivity through the singlet-triplet energy gap modulation, with the porphyrin ruffling distortion also finely tuning it. Finally, a stepwise model for the H-abstraction process is proposed which allows a direct comparison between the calculated and experimentally measured Gibbs free activation energy barriers ( Zhang et al. J. Am. Chem. Soc. 2005 , 127 , 6573 - 6582 ). The low yields in catalysis are shown not to be due to low reactivity of Mn(V).