1108678-07-4Relevant academic research and scientific papers
Imido-hydrido complexes of Mo(IV): Catalysis and mechanistic aspects of hydroboration reactions
Khalimon, Andrey Y.,Farha, Philip M.,Nikonov, Georgii I.
supporting information, p. 18945 - 18956 (2015/11/11)
Imido-hydrido complexes (ArN)Mo(H)(Cl)(PMe3)3 (1) and (ArN)Mo(H)2(PMe3)3 (2) (Ar = 2,6-diisopropylphenyl) catalyse a variety of hydroboration reactions, including the rare examples of addition of HBCat to nitriles to form bis(borylated) amines RCH2N(BCat)2. Stoichiometric reactivity of complexes 1 and 2 with nitriles and HBCat suggest that catalytic reactions proceed via a series of agostic borylamido and borylamino complexes. For complex 1, catalysis starts with addition of nitriles across the Mo-H bond to give (ArN)Mo(Cl)(NCHR)(PMe3)2; whereas for complex 2 stoichiometric reactions suggest initial addition of HBCat to form the agostic complex Mo(H)2(PMe3)3(η3-NAr-HBcat) (16).
Mechanistic aspects of hydrosilylation catalyzed by (ArN=)Mo(H)(Cl) (PMe3)3
Khalimon, Andrey Y.,Shirobokov, Oleg G.,Peterson, Erik,Simionescu, Razvan,Kuzmina, Lyudmila G.,Howard, Judith A.K.,Nikonov, Georgii I.
, p. 4300 - 4313 (2012/06/04)
The reaction of (ArN=)MoCl2(PMe3)3 (Ar = 2,6-diisopropylphenyl) with L-Selectride gives the hydrido-chloride complex (ArN=)Mo(H)(Cl)(PMe3)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 PhSiH3; however, a slow H/D exchange and formation of (ArN=)Mo(D)(Cl)(PMe3)3 (2D) was observed upon addition of PhSiD3. Reactivity of 2 toward organic substrates was studied. Stoichiometric reactions of 2 with benzaldehyde and cyclohexanone start with dissociation of the trans-to-hydride PMe3 ligand followed by coordination and insertion of carbonyls into the Mo-H bond to form alkoxy derivatives (ArN=)Mo(Cl)(OR)(PMe2)L2 (3: R = OCH2Ph, L2 = 2 PMe3; 5: R = OCH2Ph, L2 = ν2-PhC(O)H; 6: R = OCy, L2 = 2 PMe 3). The latter species reacts with PhSiH3 to furnish the corresponding silyl ethers and to recover the hydride 2. An analogous mechanism was suggested for the dehydrogenative ethanolysis with PhSiH3, 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) (ν2-CH2=CHPh)(PMe3)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.
