title: Manganese Silylene Hydride Complexes: Synthesis and Reactivity with Ethylene to Afford Silene Hydride Complexes.
abstract: Reaction of the ethylene hydride complex trans-[(dmpe)2MnH(C2H4)] (1) with Et2SiH2at 20 °C afforded the silylene hydride [(dmpe)2MnH(=SiEt2)] (2 a) as the trans-isomer. By contrast, reaction of 1 with Ph2SiH2at 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 D2afforded [(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.
authors.affiliation: Department of Chemistry, McMaster University, 1280 Main St. West, Hamilton, Ontario, L8S 4M1, Canada.
authors.forename: Jeffrey S
authors.initials: JS
authors.lastname: Price
authors.affiliation: Department of Chemistry, McMaster University, 1280 Main St. West, Hamilton, Ontario, L8S 4M1, Canada.
authors.forename: David J H
authors.identifier: 0000-0002-2570-9345
authors.initials: DJH
authors.lastname: Emslie
authors.affiliation: Department of Chemistry, McMaster University, 1280 Main St. West, Hamilton, Ontario, L8S 4M1, Canada.
authors.forename: James F
authors.initials: JF
authors.lastname: Britten
keywords: ethylene; hydride ligands; manganese; silene ligands; silylene ligands