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

ISBN-10: 0120311321

ISBN-13: 9780120311323

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RAUBENHEIMER Reaction of the complex [ O S ~ P ~ ( ~ - H ) ~ ( P(c-Hex),}] C O ) , ~ ( (148) with the affords, as the thioketene 1,1,3,3-tetrarnethyl-2-thiocarbonylcyclohexane P(c-Hex),}] (149), major product, [OS,P~~~,-S)~(~~'-C=C,H~M~~)(CO),[ which contains a ql-vinyl ligand formed by cleavage of the C=S bond of the thioketene (122). The bridging thioformamide ligand in 151 results when RN=C=S [OS~H~(CO)I~] + RN=C=S + [os,H(CO),ogl-tll-SCH=NR)] 151 (R = Me, Ph, pFC6H4, pMeC&) reacts with [Os,H,(CO),,] (123).

PhS- + $SPh Cp(CO){P(OPh)3}Fe Me 214 213 + + +SPh PhS- Cp(CO)(PPh3)Fe CH3 215 216 40 LORNA LINFORD AND HELGARD G. RAUBENHEIMER ++ PhS- + Cp(CO){P(OPh)3}Fe +Me SPh 21 e Me SPh 219 C. Reactions of Cationic Organosulfur Compounds Thioaryl chlorides, S=C( R)CI (R = pXC6H4,X = H, F, CI, Me), undergo reductive dimerization induced by [Mn(CO),]- to form E and 2 dithiolene complexes (220), which can undergo further reaction with acti- vated acetylenes or rearrange (Section II,A,2) (48). Three unexpected carbamoyl complexes (221 -223) form in the reaction of dimethylthiocarbamoyl chloride with [Cr(CO),THF], followed by chromatographic work-up (154).

Molecule and the metal atoms without affecting the double bond (283) (288). 28 3 A heterocyclic carbene complex (285) results when cyclohexasulfur is allowed to react with the ylide complex 284. The cyclization involves the incorporation of two sulfur atoms (189). 0 II C/ / O (CO15W -c4 . + ss -+ ,C--S I (COI,W=C ‘PPh3 Ph3 284 285 The anionic adduct 186, prepared from PhCZCE- (E = S or Se) and [ M(CO),(C(OEt)Ph)](M = Cr or W), adds elemental sulfur or selenium to yield heterocyclic carbene, thione, or selone complexes (286 291) after - alkylation, treatment with silica gel, or acidification with HCl (190).

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

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