Implication of a Silyl Cobalt Dihydride Complex as a Useful Catalyst for the Hydrosilylation of Imines

Bories, Cassandre C.; Barbazanges, Marion; Derat, Étienne; Petit, Marc

doi:10.1021/acscatal.1c03886

Cited by 24 publications

(28 citation statements)

References 66 publications

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“…We first evaluated Co-1 as the catalyst and phenylsilane as the hydride source . The reaction, at 50 °C, is slow with no conversion after 1 h. Extending the reaction time to 20 h drives to a conversion of 63% (Table , Entry 1).…”

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confidence: 99%

“…Our group 14 and others 15 have explored the reactivity of two simple cobalt complexes HCo(PMe 3 ) 4 and HCo(N 2 )(PPh 3 ) 3 for bonds activation, 14b−e hydroelementation, 14f,g and recently imine reduction. 16 Herein, we described for the first time an efficient 1,2-hydrosilylation of both quinolines and pyridines on a large scope using these two well-defined cobalt hydrides (Scheme 1c). 17 We first evaluated Co-1 as the catalyst and phenylsilane as the hydride source.…”

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confidence: 99%

“…17 We first evaluated Co-1 as the catalyst and phenylsilane as the hydride source. 16 The reaction, at 50 °C, is slow with no 9). In situ formation a low-valent cobalt(I) hydride Co-3 by using Co(OAc) 2 or Co(acac) 2 only led to conversion of 0% and 17%, respectively (Entry 10).…”

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Hydrido-Cobalt Complexes for the Chemo- and Regioselective 1,2-Silylative Dearomatization of N-Heteroarenes

et al. 2023

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We describe an efficient regio-and chemoselective dearomatization of N-heteroarenes using hydrido-cobalt catalysts. Reactions were performed under mild conditions on a wide range of N-heteroarenes leading exclusively to the silyl-1,2-dihydroheteroarene. Various quinolines and pyridines bearing electron-donating and electron-withdrawing substituents are compatible with this methodology. DFT calculations, NMR spectroscopic studies, and X-ray diffraction analysis underlined the importance of a second silane for the final step of the reaction.

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Hydrido-Cobalt Complexes for the Chemo- and Regioselective 1,2-Silylative Dearomatization of N-Heteroarenes

et al. 2023

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“…As a result, developing highly efficient catalysts for this type of reaction is desired. The early work of transition metal catalyzed hydrosilylation of imines is mainly based on Ru, Rh, Ir, Zn, Cu, Sn, Ti, Re, Mo, and lanthanide. , During the last decade, complexes based on Fe and Co were also investigated as catalysts for this type of reaction. , However, to the best of our knowledge, the hydrosilylation of imines catalyzed by a group 10 metal complex has rarely been explored and that catalyzed by a platinum complex has never been reported. It should be noted that platinum complexes are among the earliest used and the most effective transition metal catalysts for the hydrosilylation of olefins …”

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PNCNP Pincer Platinum Chloride Complex as a Catalyst for the Hydrosilylation of Unsaturated Carbon-Heteroatom Bonds

et al. 2022

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A PNCNP pincer-ligated platinum(II) chloride complex [2,6-( t Bu 2 PNH) 2 C 6 H 3 ]PtCl (1a) was synthesized and fully characterized. Complex 1a was applied to the catalytic hydrosilylation of unsaturated carbon-heteroatom bonds. For comparison, the corresponding hydride complex [2,6-( t Bu 2 PNH) 2 C 6 H 3 ]PtH (1b) and the related POCOP pincer chloride complex [2,6-( t Bu 2 PO) 2 C 6 H 3 ]PtCl (1c) were also used to catalyze the reactions. It was found that 1a is a good catalyst for the hydrosilylation of both C�O and C�N bonds. Wide ranges of aldimines, ketimines, aldehydes, and ketones were hydrosilylated, and the expected amine or alcohol products were obtained in good to excellent yields. The reactions also feature good functional group compatibility. Complex 1a represents the most effective transition metal catalyst for the hydrosilylation of the C�N bond and is among the best transition metal catalysts for the hydrosilylation of the C�O bond. The reactions are likely catalyzed by a cationic platinum(II) species generated from complex 1a during the reactions.

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“…Hydrosilylation of imines catalyzed by various metal catalysts has been studied extensively (such as Ti, Fe, Co, Cu, Zn, Mo, Ru, Rh, and Re); − surprisingly, only a few examples were reported so far in hydrosilylative reduction of imines catalyzed by rare-earth metal complexes. In 1997, Marks and co-workers reported organolanthanide-catalyzed imine hydrogenation using PhSiH 3 as the reductant, and the hydrosilylation product was detected in ca.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Rare-Earth Metal Complexes Bearing a 2-N,N-Dimethylamino-Ethylene-Imino-Functionalized Indolyl Ligand and Their Catalytic Activities Toward Hydrosilylation of Imines

et al. 2022

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The reactions of 2-N,N-dimethylamino-ethylene-imino-functionalized indolyl proligand 2-(Me 2 NCH 2 CH 2 N = CH)C 8 H 5 NH (HL) with [(Me 3 Si) 2 N] 3 RE(μ-Cl)Li(THF) 3 in toluene afforded a series of rare-earth metal amido complexes [κ 3 -(N,N,N)-2-(Me 2 NCH 2 CH 2 N = CH)C 8 H 5 N]RE[N(SiMe 3 ) 2 ] 2 (RE = Y (1a), Nd (1b), Sm (1c), Gd (1d), Dy (1e), Er (1f), and Yb (1g)). While the reaction of HL with [(Me 3 Si) 2 N] 3 Eu(μ-Cl)Li(THF) 3 produced the europium(II) complex in a dimeric form [{(η 5μ-η 1 :η 2), which is believed to have happened through the homolysis of the Eu−N bond. Further reaction of complex 1a with PhCH�NPh provided an unexpected rare-earth metal complex [κ 2 -(N,N)-PhN{PhCH(CH 2 SiMe 2 )}N(SiMe 3 )]YL (7) through the sp 3 C−H bond activation of the methyl on the silicon atom to form a Y−C bond followed by the insertion of the C�N bond of the imine PhCH�NPh to form an amido group connected to the central metal. All complexes were characterized by spectroscopic methods, elemental analyses, and single-crystal X-ray diffraction, and complexes 1a−1c and 7 were additionally characterized by NMR spectroscopy. The catalytic performance of complexes 1a−1g for the hydrosilylation of imines was investigated, and the catalytic mechanism was proposed based on the experimental results.

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Implication of a Silyl Cobalt Dihydride Complex as a Useful Catalyst for the Hydrosilylation of Imines

Cited by 24 publications

References 66 publications

Hydrido-Cobalt Complexes for the Chemo- and Regioselective 1,2-Silylative Dearomatization of N-Heteroarenes

Hydrido-Cobalt Complexes for the Chemo- and Regioselective 1,2-Silylative Dearomatization of N-Heteroarenes

PNCNP Pincer Platinum Chloride Complex as a Catalyst for the Hydrosilylation of Unsaturated Carbon-Heteroatom Bonds

Synthesis and Characterization of Rare-Earth Metal Complexes Bearing a 2-N,N-Dimethylamino-Ethylene-Imino-Functionalized Indolyl Ligand and Their Catalytic Activities Toward Hydrosilylation of Imines

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