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)

摘要: 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 K-edge X-ray absorption near-edge structure (XANES) extended fine-structure (EXAFS) spectroscopies. XANES for 1–3 reveals clear pre-edge features approximately +0.7 eV shift in the position `one-electron' oxidation. EXAFS simulation shows that Ni—S bond distances 1, 2 3 (2.11–2.16 A) are within typical values square planar decrease ∼0.022 A each The changes energy positions consistent with `non-innocent' character ligand. Ni—C interactions at ∼3.0 A analyzed multiple-scattering parameters also determined, leading to better overall spectra. 4 presents no feature, its shifts −0.8 eV comparison starting complex 3. Consistently, showed elongate ∼0.046 A evidence confirms neutral is `reduced' upon addition olefin, presumably olefin donating π-electron density LUMO as suggested UV/visible spectroscopy literature.