Extended X-ray absorption fine structure and multiple-scattering simulation of nickel dithiolene complexes Ni[S2C2(CF3)2]2n(n= −2, −1, 0) and an olefin adduct Ni[S2C2(CF3)2]2(1-hexene)

Abstract

A series of Ni dithiolene complexes Ni[S2C2(CF3)]2n(n= −2, −1, 0) (1,2,3) and a 1-hexene adduct Ni[S2C2(CF3)2]2(C6H12) (4) have been examined by NiK-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectroscopies. Ni XANES for1–3reveals clear pre-edge features and approximately +0.7 eV shift in the NiK-edge position for `one-electron' oxidation. EXAFS simulation shows that the Ni—S bond distances for1,2and3(2.11–2.16 Å) are within the typical values for square planar complexes and decrease by ∼0.022 Å for each `one-electron' oxidation. The changes in NiK-edge energy positions and Ni—S distances are consistent with the `non-innocent' character of the dithiolene ligand. The Ni—C interactions at ∼3.0 Å are analyzed and the multiple-scattering parameters are also determined, leading to a better simulation for the overall EXAFS spectra. The 1-hexene adduct4presents no pre-edge feature, and its NiK-edge position shifts by −0.8 eV in comparison with its starting dithiolene complex3. Consistently, EXAFS also showed that the Ni—S distances in4elongate by ∼0.046 Å in comparison with3. The evidence confirms that the neutral complex is `reduced' upon addition of olefin, presumably by olefin donating the π-electron density to the LUMO of3as suggested by UV/visible spectroscopy in the literature.