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

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

ISBN-10: 0120311321

ISBN-13: 9780120311323

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41liyl and Aryl Compleses The following scheme depicts the sequential insertion of sulfur or selenium into two W-C D bonds. Each complex can also be synthesized directly from [ WCp(CH,SiMe,),( NO)] (235); the activation bamers increase for each sequential step. The alkylperthio ligand, q2-S,R, in 237 is which makes 237 an I8e- complex, whereas 236 is regarded as a 3 ~ donor, a stable 1 6 ~ -complex. The reaction with selenium does not lead to the perseleno equivalent of 237, and only 236 and 238 can contain sulfur or selenium (159- 161).

Unexpectedly, contains a reactive thioketene function. 5). (C O),M =C /OR \ Ph + PhCECE- + 185 186 Reactions of deprotonated thioacetals, LiCHSCH,XCH,S. with the Fischer carbene complexes (185, R = Me or Et) lead to new coordinated thiocarbene ligands. The products that form (146) suggest that the lithiothioacetals display nucleophilic reactivity at two centers, the negatively charged carbon atom and a sulfur atom, each of which adds to a carbene carbon to form an adduct of type i which can undergo two types of ring opening to give the carbene complexes 187 ( X = CH, or S) and 188 ( X = S or NMe) (147).

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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