Facile C(sp2)/OR Bond Cleavage by Ru or Os

Facile C(sp2)/OR Bond Cleavage by Ru or Os

Os(H)3ClL2 (L = P i Pr3 or P t Bu2Me) are shown to be useful “precursors” to “OsHClL2”, which react with vinyl ethers to form first an η2-olefin adduct and then isomerize to the carbenes, OsHCl[CMe(OR)]L2. Subsequent R- and L-dependent reactions involve C(sp2)−OR bond cleavage, to make either carbyn...

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Veröffentlicht in:Inorganic chemistry 2001-12, Vol.40 (26), p.6610-6621
Hauptverfasser: Ferrando, German, Gérard, Hélène, Spivak, Gregory J, Coalter, Joseph N, Huffman, John C, Eisenstein, Odile, Caulton, Kenneth G
Format: Artikel
Sprache:eng
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Zusammenfassung:Os(H)3ClL2 (L = P i Pr3 or P t Bu2Me) are shown to be useful “precursors” to “OsHClL2”, which react with vinyl ethers to form first an η2-olefin adduct and then isomerize to the carbenes, OsHCl[CMe(OR)]L2. Subsequent R- and L-dependent reactions involve C(sp2)−OR bond cleavage, to make either carbyne or vinylidene complexes. The mechanisms of these reactions are explored, and the thermodynamic disparity of Ru versus Os and the influence of the OR group and the spectator phosphine ligands are discussed based on DFT (B3PW91) calculations.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic010729o