Georgii I. Nikonov

Cationic Silane σ-Complexes of Ruthenium with Relevance to Catalysis

Hydrosilylation of carbonyls catalyzed by 2 goes via intermediate formation of cationic silane sigma-complexes 4 which undergo nucleophilic abstraction of the silylium cation studied by DFT calculations.

Diversity of Catalysis by an Imido-Hydrido Complex of Molybdenum. Mechanism of Carbonyl Hydrosilylation and Silane Alcoholysis

New Imido hydride complex 1 catalyzes a variety of silylation reactions that proceed via initial substrate activation but not silane addition.

Cp(Pri2MeP)FeH2SiR3 : Nonclassical Iron Silyl Dihydride

Reactions of a new borohydride complex 2 with hydrosilanes afford half-sandwich dihydride silyl complexes 3a-f. According to X-ray and DFT evidence complexes 3 have unprecedented double H...Si...H interligand interactions.

Oxidative Addition of σ Bonds to an Al(I) Center

The Al(I) compound NacNacAl (1, NacNac = [ArNC(Me)CHC(Me)NAr](-) and Ar = 2,6-Pr(i)2C6H3) reacts with H-X (X = H, Si, B, Al, C, N, P, O) σ bonds of H2, silanes, borane (HBpin, pin = pinacolate), allane (NacNacAlH2), phosphine (HPPh2), amines, alcohol (Pr(i)OH), and Cp*H (Cp* = pentamethylcyclopentadiene) to give a series of hydride derivatives of the four-coordinate aluminum NacNacAlH(X), which are characterized herein by spectroscopic methods (NMR and IR) and X-ray diffraction. This method allows for the syntheses of the first boryl hydride of aluminum and novel silyl hydride and phosphido hydride derivatives. In the case of the addition of NacNacAlH2, the reaction is reversible, proving the possibility of reductive elimination from the species NacNacAlH(X).

Nonhydride mechanism of metal-catalyzed hydrosilylation.

A 1:1:1 reaction between complex (Tp)(ArN═)Mo(H)(PMe(3)) (3), silane PhSiD(3), and carbonyl substrate established that hydrosilylation catalyzed by 3 is not accompanied by deuterium incorporation into the hydride position of the catalyst, thus ruling out the conventional hydride mechanism based on carbonyl insertion into the M-H bond. An analogous result was observed for the catalysis by (O═)(PhMe(2)SiO)Re(PPh(3))(2)(I)(H) and (Ph(3)PCuH)(6).

Base-Catalyzed Hydrosilylation of Ketones and Esters and Insight into the Mechanism

Simple bases (KOtBu, KOH) catalyze the silane-promoted reduction of ketones and esters to alcohols and of aldimines to amines. The inexpensive silane PMHS (polymethylhydrosiloxane) can be used as the reducing reagent. Double and triple bonds, as well as nitro- and cyano-groups are tolerated. Careful dosing of the silane allows for chemoselective reduction of a more reactive group in the presence of a less reactive group (for example, aldehyde reduction in the presence of ketone/ketone reduction in the presence of ester group). Mechanistic studies showed that addition of base to silanes leads to silicate species, which are the acting reducing agents. Under basic conditions, hydrosiloxanes (tetramethyldisiloxane, TMDS; PMHS) convert into simple silanes (H2 SiMe2 , H3 SiMe), making this a practical method to generate these challenging silanes.

Facile activation of H-H and Si-H bonds by boranes.

The borane B(C(6)F(5))(3) is a precatalyst for H/Dexchange between H(2) and deuterium-labeled silanes (D(3)SiPh, D(2)SiMePh, DSiMe(2)Ph, DSiEt(3)). Experimental and DFT studies reveal that B(C(6)F(5))(3) itself cannot activate dihydrogen but converts to HB(C(6)F(5))(2) under the action of hydrosilane. The latter species easily activates H-H and Si-H bonds by a σ-bond metathesis mechanism, which was further confirmed by the reactions of BD(3)·THF with H(2).

A Coordination Compound of Ge0 Stabilized by a Diiminopyridine Ligand

Reduction of the cationic Ge(II) complex [dimpyrGeCl][GeCl3] (dimpyr=2,6-(ArN=CMe)2NC5H3, Ar=2,6-iPr2C6H3) with potassium graphite in benzene affords an air sensitive, dark green compound of Ge(0), [dimpyrGe], which is stabilized by a bis(imino)pyridine platform. This compound is the first example of a complex of a zero-valent Group 14 element that does not contain a carbene or carbenoid ligand. This species has a singlet ground state. DFT studies revealed partial delocalization of one of the Ge lone pairs over the π*(C=N) orbitals of the imines. This delocalization results in a partial multiple-bond character between the Ge atom and imine nitrogen atoms, a fact supported by the X-ray crystallography and IR spectroscopy data.

Mechanistic Aspects of Hydrosilylation Catalyzed by (ArN=)Mo(H)(Cl)(PMe3)3

The reaction of (ArN=)MoCl(2)(PMe(3))(3) (Ar = 2,6-diisopropylphenyl) with L-Selectride gives the hydrido-chloride complex (ArN=)Mo(H)(Cl)(PMe(3))(3) (2). Complex 2 was found to catalyze the hydrosilylation of carbonyls and nitriles as well as the dehydrogenative silylation of alcohols and water. Compound 2 does not show any productive reaction with PhSiH(3); however, a slow H/D exchange and formation of (ArN=)Mo(D)(Cl)(PMe(3))(3) (2(D)) was observed upon addition of PhSiD(3). Reactivity of 2 toward organic substrates was studied. Stoichiometric reactions of 2 with benzaldehyde and cyclohexanone start with dissociation of the trans-to-hydride PMe(3) ligand followed by coordination and insertion of carbonyls into the Mo-H bond to form alkoxy derivatives (ArN=)Mo(Cl)(OR)(PMe(2))L(2) (3: R = OCH(2)Ph, L(2) = 2 PMe(3); 5: R = OCH(2)Ph, L(2) = η(2)-PhC(O)H; 6: R = OCy, L(2) = 2 PMe(3)). The latter species reacts with PhSiH(3) to furnish the corresponding silyl ethers and to recover the hydride 2. An analogous mechanism was suggested for the dehydrogenative ethanolysis with PhSiH(3), with the key intermediate being the ethoxy complex (ArN=)Mo(Cl)(OEt)(PMe(3))(3) (7). In the case of hydrosilylation of acetophenone, a D-labeling experiment, i.e., a reaction of 2 with acetophenone and PhSiD(3) in the 1:1:1 ratio, suggests an alternative mechanism that does not involve the intermediacy of an alkoxy complex. In this particular case, the reaction presumably proceeds via Lewis acid catalysis. Similar to the case of benzaldehyde, treatment of 2 with styrene gives trans-(ArN=)Mo(H)(η(2)-CH(2)═CHPh)(PMe(3))(2) (8). Complex 8 slowly decomposes via the release of ethylbenzene, indicating only a slow insertion of styrene ligand into the Mo-H bond of 8.

The unexpected mechanism of carbonyl hydrosilylation catalyzed by (Cp)(ArN[double bond, length as m-dash])Mo(H)(PMe(3)).

Complex (Cp)(ArN[double bond, length as m-dash])Mo(H)(PMe(3)) (2, Ar = 2,6-diisopropylphenyl) catalyzes the hydrosilylation of carbonyls by an unexpected associative mechanism. Complex 2 also reacts with PhSiH(3) by a σ-bond metathesis mechanism to give the silyl derivative (Cp)(ArN[double bond, length as m-dash])Mo(SiH(2)Ph)(PMe(3)).