By F.G.A. Stone, Robert West (Eds.)
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Extra info for Advances in Organometallic Chemistry, Vol. 32
Bonds are A complication arises when R1R2is CH,N(Me)CH2; two C-S cleaved and the sulfur atoms are alkylated (141). OEt I Iron pentacarbonyl reacts with a-thiocarbanions to form 181 (R'= Ph or p-MeC,H,, R2= Ph or CH=CH,) and then with methyl iodide to produce P-keto sulfides, together with some dithioethers and stilbene (R2= Ph). The use of an acid chloride (R3 = CHMe,, CH=CHMe, Ph, C&O) as the electrophile leads to the formation of thioesters (142). When the substituted iron carbonyl [Fe(CO),PPh,] is treated with LiCH(SPh)CH,Bu and [OEt3][BF,], the iron carbene complex [Fe(CO),(C(OEt)CH(SPh)CH,Bu)(PPh3)](182) can be prepared (143).
Me 197 196 3. 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).
R = 266 267 CH,Bu' or p-MeC,H,]. The reaction is considered to be charge controlled and to proceed via electrophilic attack by S, on the carbyne carbon ( I 78). An additional complex (267, M = W, E = S , L=CO, R = Me) can be obtained from [ W=CMe(Cp)(CO),] and cyclohexenesulfide ( I 79). With the osmium complex 268 ( R = p-tolyl), however, reaction with sulfur does not proceed beyond the $-thioacyl complex (269, E = S or Se). Selenoand telluroacyl complexes result from analogous reactions (180).
Advances in Organometallic Chemistry, Vol. 32 by F.G.A. Stone, Robert West (Eds.)