Multiple Bonding Between Main-Group And Transition Elements

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Abstract
The reaction of (Me3Si)2 CHBiCl2 with K2 [W(CO)5] results in tungsten/bismuth cluster compounds. The reaction of (Me3Si)2 CHSbCl)2, with Na2(Fe(CO)4] affords an η2-distibene complex which, in turn, reacts with Fe2(CO)9 to produce Fe2(μ-SbCH(SiMe3),2)(CO)8, a “closed” (i.e. metal-metal bonded) stibinidene complex. The reaction of (2,4,6-t-Bu3C6H2)PCl2 with Na[Co2(μ2-CO)2 (η-C5H5)2] produces 2,4,6-t-Bu3C6H2)-P[Co(CO)(η-C5H5) 2, an “open” phosphinidene complex. The factors affecting the “open” or “closed” nature of dimetallic phosphinidene (or heavier congeneric) complexes are discussed. The discussion is extended from sixteen-electron to fifteen-or fourteen-electron organometallic fragments. The synthesis of Co2 (μ-P(2,4,6-t-Bu3C6H2))(CO)6, a three-membered ring with Co—P multiple bonding is discussed. Finally, the reaction of the phosphaketene, (2,4,6-t-Bu3C6H2)P=C=O, with Fe2 (CO)9 is described.

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