By F.G.A. Stone, Robert West (Eds.)
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Extra info for Advances in Organometallic Chemistry, Vol. 32
L t r 121 122 IV REACTIONS OF ORGANOSULFUR COMPOUNDS WITH ORGANOMETALLIC COMPLEXES This section focuses on the interactions between organosulfur compounds and coordinated ligands and, linking up with Section 11, on the fragmentations of organosulfur compounds by metal carbonyls. A. Neutral Organosulfur Compounds 1. Thioerhers Thioethers add reversibly to carbene complexes 123 and 126 to give + 123 124 H 125 sulfur ylide, 124 [R = Me, Et; R2 = -(CH,),--] or sulfonium salt, 127 [R = Me, CH2Ph, CH,ReCp(NO)(PPh,)], complexes.
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).
M iscellunCONS A doubly bridging thiolate ligand in 278 results from the reaction of 277 with elemental sulfur. In effect, the N donor group is replaced by sulfur, and a sulfur atom is inserted into the original Fe-C o bond (184). s s ( C 0 ) 3 F e -Fe(C0I3 27 7 + S, + l,Y \ -Fe(C0)3 (C0I3Fe- 278 reaction of allyltrimethylsilane with elemental sulfur in the presence of triiron dodecacarbonyl leads to the addition of sulfur at an olefinic double bond and the formation of 279. No reaction occurs in the absence of CHzSiMe3 I 279 58 LORNA LINFORD AND HELGARD 0.