Despite being known since 1961, the chemistry of carbodiphosphoranes, C(PR3)2, has remained relatively unexplored until recently. An interesting feature of C(PR3)2 is that the carbon atom is formally zerovalent and possesses two lone pairs of electrons, such that the geometry is bent. However, we have demonstrated that C(PPh3)2 can exist in a linear form, which is in marked contrast to the bent geometries that have been previously reported, with P–C–P bond angles of 130, 132, and 144 degrees. The bonding within C(PPh3)2 has been examined by density functional theory calculations which demonstrate that the energy surface for bending the P–C–P bonds is very shallow. In view of the presence of the lone pairs on carbon, C(PPh3)2 may serve as a ligand for metals and here we describe its role in main group metal alkyl chemistry.

Flexible nature of the carbodiphosphorane, C(PPh3)2, and its reactivity towards main group alkyl complexes

255th National Meeting (2018)

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