Mechanistic aspects of hydrosilylation catalyzed by (ArN=)Mo(H)(Cl) (PMe 3) 3

Andrey Y. Khalimon, Oleg G. Shirobokov, Erik Peterson, Razvan Simionescu, Lyudmila G. Kuzmina, Judith A K Howard, Georgii I. Nikonov

Research output: Contribution to journalArticle

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Abstract

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 2Ph, L 2 = 2 PMe 3; 5: R = OCH 2Ph, L 2 = ν 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) (ν 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.

Original languageEnglish
Pages (from-to)4300-4313
Number of pages14
JournalInorganic Chemistry
Volume51
Issue number7
DOIs
Publication statusPublished - Apr 2 2012
Externally publishedYes

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Hydrosilylation
Styrene
Hydrides
Ligands
Lewis Acids
Nitriles
Ethers
Labeling
Catalysis
Chlorides
styrenes
Alcohols
hydrides
insertion
Derivatives
Water
Substrates
ligands
nitriles
Experiments

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Khalimon, A. Y., Shirobokov, O. G., Peterson, E., Simionescu, R., Kuzmina, L. G., Howard, J. A. K., & Nikonov, G. I. (2012). Mechanistic aspects of hydrosilylation catalyzed by (ArN=)Mo(H)(Cl) (PMe 3) 3 . Inorganic Chemistry, 51(7), 4300-4313. https://doi.org/10.1021/ic300010c

Mechanistic aspects of hydrosilylation catalyzed by (ArN=)Mo(H)(Cl) (PMe 3) 3 . / Khalimon, Andrey Y.; Shirobokov, Oleg G.; Peterson, Erik; Simionescu, Razvan; Kuzmina, Lyudmila G.; Howard, Judith A K; Nikonov, Georgii I.

In: Inorganic Chemistry, Vol. 51, No. 7, 02.04.2012, p. 4300-4313.

Research output: Contribution to journalArticle

Khalimon, AY, Shirobokov, OG, Peterson, E, Simionescu, R, Kuzmina, LG, Howard, JAK & Nikonov, GI 2012, 'Mechanistic aspects of hydrosilylation catalyzed by (ArN=)Mo(H)(Cl) (PMe 3) 3 ', Inorganic Chemistry, vol. 51, no. 7, pp. 4300-4313. https://doi.org/10.1021/ic300010c
Khalimon AY, Shirobokov OG, Peterson E, Simionescu R, Kuzmina LG, Howard JAK et al. Mechanistic aspects of hydrosilylation catalyzed by (ArN=)Mo(H)(Cl) (PMe 3) 3 . Inorganic Chemistry. 2012 Apr 2;51(7):4300-4313. https://doi.org/10.1021/ic300010c
Khalimon, Andrey Y. ; Shirobokov, Oleg G. ; Peterson, Erik ; Simionescu, Razvan ; Kuzmina, Lyudmila G. ; Howard, Judith A K ; Nikonov, Georgii I. / Mechanistic aspects of hydrosilylation catalyzed by (ArN=)Mo(H)(Cl) (PMe 3) 3 . In: Inorganic Chemistry. 2012 ; Vol. 51, No. 7. pp. 4300-4313.
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title = "Mechanistic aspects of hydrosilylation catalyzed by (ArN=)Mo(H)(Cl) (PMe 3) 3",
abstract = "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 2Ph, L 2 = 2 PMe 3; 5: R = OCH 2Ph, L 2 = ν 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) (ν 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.",
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T1 - Mechanistic aspects of hydrosilylation catalyzed by (ArN=)Mo(H)(Cl) (PMe 3) 3

AU - Khalimon, Andrey Y.

AU - Shirobokov, Oleg G.

AU - Peterson, Erik

AU - Simionescu, Razvan

AU - Kuzmina, Lyudmila G.

AU - Howard, Judith A K

AU - Nikonov, Georgii I.

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N2 - 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 2Ph, L 2 = 2 PMe 3; 5: R = OCH 2Ph, L 2 = ν 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) (ν 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.

AB - 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 2Ph, L 2 = 2 PMe 3; 5: R = OCH 2Ph, L 2 = ν 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) (ν 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.

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