Probing Substituent Effect on Nickel-Sulfur Bond Covalency in Ni(II)-Dithiophosphinate Complexes by Sulfur K-Edge XAS and DFT Calculations.

Complexes of Ni(II) with a series of aryl or alkyl substituent dithiophosphinic acids were characterized by crystallographic structure, sulfur K-edge X-ray absorption spectroscopy (XAS), and density functional theory (DFT). In these complexes, Ni(II) coordinates with four sulfur atoms from two dithiophosphinate anions form a well-defined square-planar structure. Despite the minor differences in the geometry parameters among the complexes, the electronic structure is affected significantly by the substituent group attached to dithiophosphinic acid. In particular, the addition of -CF group to the aryl ring constrains the orientation of the aryl ring and enhances the conjugation between the aryl ring and the coordinating core. Sulfur K-edge XAS spectra help further reveal the electronic structure of the complexes. Both the pre-edge feature and rising-edge feature provide abundant information on the molecular orbitals and show a distinctive effect of the substituent groups on the electronic structure of the complexes, which is supposedly relevant to the ligand's performance in Ln(III)/An(III) separation.