Inorganic Chemistry, Vol.46, No.22, 9146-9154, 2007
A pnictogen of peculiar posture
In 2001, Bridgeman et al. synthesized a rare species having a T-shaped phosphorus atom centering an organometallic cluster, [{Cp(OC)(2)Mo}(2)PMn(CO)(4)]- Our DFT and extended Huckel electronic structure calculations indicate that the T-shaped geometry results from an unusual Mo-Mn-Mo three-center, two-electron bond that "ties" back the two-center, two-electron Mo-P bonds. Additional stabilization of the planar structure arises from Mo-P pi backdonation in a three-center, four-electron Mo-P-Mo pi bond. We find that this compound best resembles a mu(2-)phosphinidene system, and we also attempt to reconcile 18- and 8-electron rule considerations with the delocalized bonding in this intriguing cluster.