Electronic properties of Strandberg anions: A DFT study of [X2Mo5O23]n−, (X = PV,SVI, AsV,SeVI), and [(RP)2Mo5O21]4− (R = H,CH3, C2H5)

The electronic properties of the anions mentioned in the title polyanions were calculated by means of Density Functional Theory (DFT). The redox properties and the basicity of the external oxygen sites of those polyanions were analyzed. The results show that the redox properties of Strandberg anions depend on the nature of heteroatom X. The organic group bonded to the heteroatom modifies the redox property of the cluster. The oxygen basicities of the polyanions were analyzed by virtue of molecular electrostatic potential (MEP). The MEP distribution suggests that the most basic centers are triple‐bridging oxygen atoms, one of which is shared with two metal atoms and one heteroatom X in [P₂Mo₅O₂₃]^6? and [As₂Mo₅O₂₃]^6?. In [(RP)₂Mo₅O₂₁]^4?, the triple‐bridging oxygen atoms and the double‐bridging oxygen atoms bonded to two Mo atoms identified as the most basic centers. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005