Probing the electronic structure of [MoOS(4)](-) centers using anionic photoelectron spectroscopy.
Probing the electronic structure of [MoOS(4)](-) centers using anionic photoelectron spectroscopy.
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使用阴离子光电子能谱探测 [MoOS(4)](-) 中心的电子结构。
DOI：
10.1021/ja0265557
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发表时间：
2002
影响因子：
15
通讯作者：
Wang,Lai-Sheng
中科院分区：
文献类型：
--
作者：
Wang,Xue-Bin;Inscore,FrankE;Yang,Xin;Cooney,JJonA;Enemark,JohnH;Wang,Lai-Sheng
在气相中使用光脱离光电子能谱 (PES)，我们研究了六种阴离子 [MoVO]3+ 配合物、[MoOX4]-（其中 X = Cl (1)、SPh (2) 和 SPh-p-Cl (3)）、[MoO(edt)2]-(4)、[MoO(bdt)2]-(5) 和[MoO(bdtCl2)2]-(6)（其中 edt = 乙烷-1,2-二硫醇盐，bdt = 苯-1,2-二硫醇盐，bdtCl2= 3,6-二氯苯-1,2-二硫醇盐）。气相 PES 数据揭示了有关 [MoVO]3+ 配合物的大量新电子结构信息。观察到最高占据分子轨道 (HOMO) 和 HOMO−1 之间的能量间隔取决于 O−Mo−S−C(α) 二面角和配体类型，单齿配体相对较大，Cl 为 1.32 eV，SPh 和 SPhCl 为 0.78 eV，而双齿二硫醇盐配合物的能量间隔（edt 为 0.47 eV，SPh 为 0.44 eV） bdt 和 bdtCl2。所有六个物种的阈值 PES 特征显示出具有相同的起源，并且是由于 HOMO 中单个不成对电子的分离，主要具有 Mo 4d 特征。该结果与之前的理论计算一致，并通过与两个d0配合物[VO(bdt)2]-和[VO(bdtCl2)2]-的PES谱比较得到验证。观察到的 PES 特征是根据理论计算和先前凝聚相光谱研究来解释的。
Using photodetachment photoelectron spectroscopy (PES) in the gas phase, we investigated the 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). The gas-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−1 were observed to be dependent on the O−Mo−S−C(α) dihedral angles and ligand types, being relatively large for the monodentate ligands, 1.32 eV for Cl and 0.78 eV for SPh and SPhCl, compared to those of the bidentate dithiolate complexes, 0.47 eV for edt and 0.44 eV for bdt and bdtCl2. The threshold PES feature in all six species is shown to have the same origin and is due to detaching the single unpaired electron in the HOMO, mainly of Mo 4d character. This result is consistent with previous theoretical calculations and is verified by comparison with the PES spectra of two d0complexes, [VO(bdt)2]-and [VO(bdtCl2)2]-. The observed PES features are interpreted on the basis of theoretical calculations and previous spectroscopic studies in the condensed phase.