Probing the Electronic Structure of [MoOS4]- Centers Using Anionic Photoelectron Spectroscopy
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- 作者：Xue-Bin Wang ; Frank E. Inscore ; Xin Yang ; J. Jon A. Cooney ; John H. Enemark ; and Lai-Sheng Wang
- 刊名：Journal of the American Chemical Society
- 出版年：2002
- 出版时间：August 28, 2002
- 年：2002
- 卷：124
- 期：34
- 页码：10182 - 10191
- 全文大小：205K
- 年卷期：v.124,no.34(August 28, 2002)
- ISSN：1520-5126
文摘
Using photodetachment photoelectron spectroscopy (PES) in the gas phase, we investigatedthe electronic structure and chemical bonding of six anionic [MoVO]3+ complexes, [MoOX4]- (where X = Cl(1), SPh (2), and SPh-p-Cl (3)), [MoO(edt)2]- (4), [MoO(bdt)2]- (5), and [MoO(bdtCl2)2]- (6) (where edt =ethane-1,2-dithiolate, bdt = benzene-1,2-dithiolate, and bdtCl2 = 3,6-dichlorobenzene-1,2-dithiolate). Thegas-phase PES data revealed a wealth of new electronic structure information about the [MoVO]3+complexes. The energy separations between the highest occupied molecular orbital (HOMO) and HOMO-1were observed to be dependent on the O-Mo-S-C(
ages/gifchars/alpha.gif" BORDER=0>) dihedral angles and ligand types, being relativelylarge for the monodentate ligands, 1.32 eV for Cl and 0.78 eV for SPh and SPhCl, compared to those ofthe bidentate dithiolate complexes, 0.47 eV for edt and 0.44 eV for bdt and bdtCl2. The threshold PESfeature in all six species is shown to have the same origin and is due to detaching the single unpairedelectron in the HOMO, mainly of Mo 4d character. This result is consistent with previous theoreticalcalculations and is verified by comparison with the PES spectra of two d0 complexes, [VO(bdt)2]- and[VO(bdtCl2)2]-. The observed PES features are interpreted on the basis of theoretical calculations andprevious spectroscopic studies in the condensed phase.