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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. [ABSTRACT FROM AUTHOR]

Die Reaktionen, die D. J. H. Emslie et al. in ihrer Zuschrift auf S. 6319 ff. vorstellen, starten bei Mangan und Wasserstoff und führen nacheinander Silicium und Kohlenstoff ein, bereitgestellt von dem im Vordergrund gezeigten Inukshuk, einem von den Bewohnern der arktischen Regionen Nordkanadas genutzten Steinwegweiser. Im Hintergrund erklimmen zwei Silylenhydrid ‐ Moleküle den Gipfel der “Hounds Tooth” in British Columbia (Kanada), auf dem das Reaktionsprodukt thront. [ABSTRACT FROM AUTHOR]