Interconversion and reactivity of manganese silyl, silylene, and silene complexes

Abstract

Manganese disilyl hydride complexes [(dmpe)₂MnH(SiH₂R)₂] (4^Ph: R = Ph, 4^Bu: R = ⁿBu) reacted with ethylene to form silene hydride complexes [(dmpe)₂MnH(RHSiCHMe)] (6^Ph,H: R = Ph, 6^Bu,H: R = ⁿBu). Compounds 6^R,H reacted with a second equivalent of ethylene to generate [(dmpe)₂MnH(REtSiCHMe)] (6^Ph,Et: R = Ph, 6^Bu,Et: R = ⁿBu), resulting from apparent ethylene insertion into the silene Si–H bond. Furthermore, in the absence of ethylene, silene complex 6^Bu,H slowly isomerized to the silylene hydride complex [(dmpe)₂MnH(SiEtⁿBu)] (3^Bu,Et). Reactions of 4^R with ethylene likely proceed via low-coordinate silyl {[(dmpe)₂Mn(SiH₂R)] (2^Ph: R = Ph, 2^Bu: R = ⁿBu)} or silylene hydride {[(dmpe)₂MnH(SiHR)] (3^Ph,H: R = Ph, 3^Bu,H: R = ⁿBu)} intermediates accessed from 4^R by H₃SiR elimination. DFT calculations and high temperature NMR spectra support the accessibility of these intermediates, and reactions of 4^R with isonitriles or N-heterocyclic carbenes yielded the silyl isonitrile complexes [(dmpe)₂Mn(SiH₂R)(CNR′)] (7a–d: R = Ph or ⁿBu; R′ = o-xylyl or ^tBu), and NHC-stabilized silylene hydride complexes [(dmpe)₂MnH{SiHR(NHC)}] (8a–d: R = Ph or ⁿBu; NHC = 1,3-diisopropylimidazolin-2-ylidene or 1,3,4,5-tetramethyl-4-imidazolin-2-ylidene), respectively, all of which were crystallographically characterized. Silyl, silylene and silene complexes in this work were accessed via reactions of [(dmpe)₂MnH(C₂H₄)] (1) with hydrosilanes, in some cases followed by ethylene. Therefore, ethylene (C₂H₄ and C₂D₄) hydrosilylation was investigated using [(dmpe)₂MnH(C₂H₄)] (1) as a pre-catalyst, resulting in stepwise conversion of primary to secondary to tertiary hydrosilanes. Various catalytically active manganese-containing species were observed during catalysis, including silylene and silene complexes, and a catalytic cycle is proposed.