Sulfur K-edge X-ray absorption spectroscopy as a probe of ligand-metal bond covalency: Metal vs ligand oxidation in copper and nickel dithiolene complexes

被引:168
作者
Sarangi, Ritimukta
George, Serena DeBeer [1 ]
Rudd, Deanne Jackson
Szilagyi, Robert K.
Ribas, Xavi
Rovira, Concepcio
Almeida, Manuel
Hodgson, Keith O.
Hedman, Britt
Solomon, Edward I.
机构
[1] Stanford Univ, Stanford Linear Accelerator Ctr, Stanford Synchrotron Radiat Lab, Stanford, CA 94309 USA
[2] Stanford Univ, Dept Chem, Stanford, CA 94305 USA
[3] Univ Autonoma Barcelona, Inst Ciencia Mat Barcelona, Bellaterra 08193, Spain
[4] UL, CFMC, Dept Quim, Inst Tecnol & Nucl, P-2686953 Sacavem, Portugal
关键词
D O I
10.1021/ja0665949
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A combination of Cu L-edge and S K-edge X-ray absorption data and density functional theory (DFT) calculations has been correlated with S-33 electron paramagnetic resonance superhyperfine results to obtain the dipole integral (I-s) for the S 1s -> 3p transition for the dithiolene ligand maleonitriledithiolate (MNT) in (TBA)(2)[Cu(MNT)(2)] (TBA) tetra-n-butylammonium). The results have been combined with the I-s of sulfide derived from XPS studies to experimentally obtain a relation between the S 1s -> 4p transition energy (which reflects the charge on the S atom, Q mol S) and the dipole integral over a large range of Q mol S. The results show that, for high charges on S, I-s can vary from the previously reported I-s values, calculated using data over a limited range of Q mol S. A combination of S K-edge and Cu K-and L-edge X-ray absorption data and DFT calculations has been used to investigate the one-electron oxidation of [Cu(MNT)2](2)-and [Ni(MNT)(2)](2-). The conversion of [Cu(MNT)(2)](2)-to [Cu(MNT)(2)]-results in a large change in the charge on the Cu atom in the molecule (Q mol Cu) and is consistent with a metal-based oxidation. This is accompanied by extensive charge donation from the ligands to compensate the high charge on the Cu in [Cu(MNT) 2]based on the increased S K-edge and decreased Cu L-edge intensity, respectively. In contrast, the oxidation of [Ni(MNT) 2] 2-to [Ni(MNT) 2]-results in a small change in Q mol Ni, indicating a ligand-based oxidation consistent with oxidation of a molecular orbital, psi*(SOMO) (singly occupied molecular orbital), with predominant ligand character.
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页码:2316 / 2326
页数:11
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