CHEMISTRY OF TRIVALENT URANIUM METALLOCENES - ELECTRON-TRANSFER REACTIONS WITH CARBON-DISULFIDE - FORMATION OF [(RC5H4)3U]2[MU-ETA-1,ETA-2-CS2]
CHEMISTRY OF TRIVALENT URANIUM METALLOCENES - ELECTRON-TRANSFER REACTIONS WITH CARBON-DISULFIDE - FORMATION OF [(RC5H4)3U]2[MU-ETA-1,ETA-2-CS2]
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DOI：
10.1021/ic00231a007
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发表时间：
1986-05-21
影响因子：
4.6
通讯作者：
ZALKIN, A
中科院分区：
文献类型：
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作者：
BRENNAN, JG;ANDERSEN, RA;ZALKIN, A
结论本项目实现了 Nin/PtIV 卤桥链配合物的分离和光谱表征，与已经表征的 Ptn/PtIV、Pdn/Pdlv 和 Pdn/PtIV 直接类似。 Mn/MIV 配合物的能量通常如图 9a 所示；简并基态 Mn/MIV 和 MIV/Mn 可通过对称激发态 Mln/Mm 通过连续的单电子转移进行相互转换，并伴随着卤素原子沿卤素-金属坐标 Ql（产生长共振拉曼级数的模式）的适当位移。对于纯金属配合物，卤素预计位于 Mm/Mnl 态的中心，但对于混合金属类似物则不然。对于混合金属配合物的能量学，可以设想三种可能的情况（参见图 9）。第一种情况（图 9a）对应于 Mn/Ptlv 和 MIV/Ptn（M= Ni、Pd）具有相同能量的情况。对于 = Pd, Ni，这是极不可能的；事实上，对于本项目和其他地方研究的所有混合金属配合物，Mn/PtIV 均被确定为基态。在剩下的两个案例中（图 9b、c），我们的预期是图 9c 最好地代表了这种情况，MIV/Ptn 状态的实际人口实际上为零。
ConclusionThe present project has led to the isolation and the spectral characterization of Nin/PtIV halogen-bridged chain complexes, directly analogous to the Ptn/PtIV, Pdn/Pdlv, and Pdn/PtIV ones already characterized. The energetics of the Mn/MIV complexes are usually represented as in Figure 9a; the degenerate ground states Mn/MIV and MIV/Mn are interconvertible via the sym-metric excitedstate Mln/Mm by successive one-electron transfers and are accompanied by suitable displacement of the halogen atom along the halogen-metal coordinate, Ql (the mode giving riseto the long resonance Raman progressions). The halogen would be expected to the centrally placed in the Mm/Mnl state for the pure metal complexes, but not for the mixed-metal analogues. Three possible cases can beenvisaged for the energetics of the mixedmetal complexes (cf. Figure 9). The first case (Figure 9a) cor-responds to that in which both Mn/Ptlv and MIV/Ptn (M= Ni, Pd) have the same energy. This is highly unlikely for= Pd, Ni; indeed, for all mixed-metal complexes studied in this project and elsewhere, Mn/PtIV is established to be the ground state. Of the two remaining cases (Figure 9b, c) our expectation is that the situation is best represented by Figure 9c, the actual population of the MIV/Ptn state beingeffectively zero.