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

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

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The thioether ligand in 127 ( R = Me) is displaced by the nucleophile MeS-, and 128, which is the complex used to produce the dinuclear sulfonium salt form of 127 [R = CH,ReCp(NO)(PPh,)], forms (108). The cationic ylide complex 130 is formed when SMe, adds to the carbenoid ligand in I29 (109). + CP I 129 130 and [ Fe(CO),] causes the coupling of two molecules of acetylene and the formation of a ferrole complex (131) (110). SMe I 131 Low-valent nickel species catalyze the reaction between Grignard reagents and aryl or alkenyl sulfide in the preparation of alkylarenes.

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). 5). 35 bond of 139 gives the thiolate complexes (140) Cp,Zr(H)CI + R2C=S - Cp,Zr(CI)SCHR, 139 I40 Substituted thiobenzophenones react with anionic manganese carbonyl and abstract H+ from the solvent (MeOH/H,O) to form the dinuclear bridging complexes, 141 (R = H, Me, NMe,, F, OMe) ( I 16).

S ( ? f . 4 c e t j h ~ n1'inylidme. ~. und Allone Gompfews A series of alkenyl complexes (214, 216, and 218) were prepared from the reaction of PhS- with the alkyne complex 213, the q2-allene complex 215, and the cationic complex 217. Complex 218, with the nucleophile linked at the cy position, could be converted to an allenacyl complex (219) by the addition of CO and a catalytic amount of oxidant, such as [Cp,Fe][ BF,] or Ce'"/EtOH. Excess Ce'"/EtOH leads to the formation of an alkenyl ester, (EtO)C(O)C(Me)=C( Me)SPh (153).

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