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

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

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Additional resources for Advances in Organometallic Chemistry, Vol. 32

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S [(MeC5H,)(CO)p Mn G C P h ] I1 + I ii LiCNMep CH3COOH > /Ph (MeC5H4)(CO)2 Mn-S=C 'scH2 cNMe2 II S 211 210 t { ( Me C5H4 1(CO)pMn}p (p - S) 21 2 4. 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.

RAUBENHEIMER PPh,, PMe,Ph, or C6HI,NC, R =p-MeOC,H, or C,H,,) and thiirane, which yields cyclic aminothiocarbene complexes (166). Thiirane does not react with the bulky Bu‘NC ligand (Z3Z). The thermal fragmentation of thiirane or thiirane S-oxide in the presence of [ Fe,(CO),,] yields the ethenedithiolate complex, 3a, by incorporating an additional sulfur atom into I I s\ / s 0 Fe 3( C 01, II + /”\ I + I/\\ -Fe(C013 (C013Fe . the ligand (132). The same occurs when ethylene sulfide, SCH,CHR (R = H), or propylene sulfide (R = Me) reacts with [MoHCp(CO),] or [ MoCp(CO),], (CpMoL,) to give 168.

Reaction of 118 with methylhydrazine produces mainly an NMe- or EtO \ (CO) M=C 5 1: M = Cr Et' /OEt ,OEt -c\\ (CO)qM, ,C-H H H ' 117 tie (CO) M=C /OEt \ H c=c ' /H \S[CH2I3 SEt 119 NH-inserted seven-membered chelate product, but a rearrangement product, 120, also forms in which carbene insertion into a C-S bond effected 120 32 LORNA LINFORD AND HELGARD G. RAUBENHEIMER coordination of this sulfur atom at the vacated coordination site. Finally, deprotonation of the C-methyl group of the carbene complex 121 leads to the neutral methylthiovinyl tungsten complex, 122 (106).

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