4 years ago

Manganese Silylene Hydride Complexes: Synthesis and Reactivity with Ethylene to Afford Silene Hydride Complexes

Manganese Silylene Hydride Complexes: Synthesis and Reactivity with Ethylene to Afford Silene Hydride Complexes
Jeffrey S. Price, David J. H. Emslie, James F. Britten
Reaction of the ethylene hydride complex trans-[(dmpe)2MnH(C2H4)] (1) with Et2SiH2 at 20 °C afforded the silylene hydride [(dmpe)2MnH(=SiEt2)] (2 a) as the trans-isomer. By contrast, reaction of 1 with Ph2SiH2 at 60 °C afforded [(dmpe)2MnH(=SiPh2)] (2 b) as a mixture of the cis (major) and trans (minor) isomers, featuring a Mn-H-Si interaction in the former. The reaction to form 2 b also yielded [(dmpe)2MnH2(SiHPh2)] (3 b); [(dmpe)2MnH2(SiHR2)] (R=Et (3 a) and Ph (3 b)) were accessed cleanly by reaction of 2 a and 2 b with H2, and the analogous reactions with D2 afforded [(dmpe)2MnD2(SiHR2)] exclusively. Both 2 a and 2 b engaged in unique reactivity with ethylene, generating the silene hydride complexes cis-[(dmpe)2MnH(R2Si=CHMe)] (R=Et (4 a), Ph (4 b)). Compounds trans-2 a, cis-2 b, 3 b, and 4 b were crystallographically characterized, and bonding in 2 a, 2 b, 4 a, and 4 b was probed computationally. Alkene hydride complex trans-[(dmpe)2MnH(C2H4)] eliminates ethane upon reaction with secondary silanes, yielding cis- and trans-isomers of the silylene hydride complexes [(dmpe)2MnH(=SiR2)]. Reaction with ethylene yields silene hydride complexes [(dmpe)2MnH(R2Si=CHMe)]—most likely via a low-coordinate silyl isomer [(dmpe)2Mn(SiHR2)] that is in equilibrium with the silylene hydrides.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201700863

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