Advances in Organometallic Chemistry, Vol. 32 by F.G.A. Stone, Robert West (Eds.) PDF

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By F.G.A. Stone, Robert West (Eds.)

ISBN-10: 0120311321

ISBN-13: 9780120311323

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SEt ( C O ) w =c 5 \ SiPh3 - 73 Et S ‘c=c=o Ph3Si / 74 + (CO),W--S / Et \ P h3Si /c=c=o 75 E. Metallacycles Carbonylselenide is ejected from the metallacyclic compound 76 when heated to give a selenoformaldehyde compound, 77 (86). An example of a 24 LORNA LINFORD AND HELGARD G. RAUBENHEIMER H\ / H ,C-0 (C 0l2( P P h3 I2O s I \Se/ 3 (C0)JPPh c=se + 1 Os’l 32 COSe ‘se 77 76 spontaneous decarbonylation (in THF) of an organosulfur chelate is provided by the heterometallacycle 78, affording 79 (87).

Reudions if \ SMe Carbjwc Complrses Nucleophiljc displacement at a terminal methylidyne ligand, with regeneration of a metal -carbon triple bond in 199 (E = S or Se, R = Me, Ph, or p-N02C,H,) to form a new methylidyne ligand, occurs in the reaction of 198 [ L = HB(3,5-Me2-C3HN2),] with thiolate or selenolate anions under phase-transfer conditions (149). L(C0)2M~EC--CI + RE- + L(C0)2M~SC-ER 198 199 The reaction of nucleophiles, RE- (ER = SMe, SPh, CH2Ph, SePh), with the bridging thiocarbyne ligand in 200 leads to bridging carbene complexes (201).

132 133 34 LORNA LINFORD AND HELGARD G. RAUBENHEIMER 2. Thioketones, Isothiocyanates. and Thioketenes The reactions of thiobenzophenone are vaned. In the imidoylcobalt-acetone adduct 134, it displaces the acetone to form complex 135, which is t t Ph2C=S _j Me3P’ 135 134 structurally similar to 134 (112). The reaction with [Os,H,(CO),( NMe,)] depends on the speed at which thiobenzophenone is added to the reaction mixture. When reacted with [Os,H,(CO),,], only the latter type of conversion occurs to give 138 (114).

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Advances in Organometallic Chemistry, Vol. 32 by F.G.A. Stone, Robert West (Eds.)

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