Abstract

The 32-electron benzylidyne-bridged complex [Mo2Cp2(μ-CPh)(μ-PCy2)(CO)2] reacted with elemental chalcogens En (E = S, Se) at 333 K to give the corresponding derivatives trans-[Mo2Cp2{μ-η2:η2-C(Ph)E}(μ-PCy2)(CO)2], following from addition of a chalcogen atom to the Mo2C face of the central Mo2PC core in the parent compound, whereby a 5-electron donor, bridging chalcogenoacyl ligand was formed (Mo−Mo = 2.8662(5) Å, C−S = 1.757(5) Å in the thioacyl complex). These thermally stable products did not undergo decarbonylation under irradiation with visible-UV light, but instead rearranged into the corresponding cis-dicarbonyl isomers cis-[Mo2Cp2{μ-η2:η2-C(Ph)E}(μ-PCy2)(CO)2] (Mo−Mo = 2.9208(5) Å, C−S = 1.745(5) Å in the thioacyl complex), in a process where no reaction intermediates were detected. The coordination of the chalcogenoacyl ligand in the cis-dicarbonyl isomers is analogous to that observed in the corresponding trans isomers, and involves the selective positioning of the 3-electron donor chalcogen atom trans to the bridging phosphanyl ligand, a structural trend common to related complexes with isoelectronic η2:η2 bridging groups such as iminoacyl, formimidoyl and diphosphenyl ligands.

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