Di- and trinuclear complexes with sulfide-bridged rhenium in very different oxidation states (ReIReVII, ReIReVIReI, ReIReVIIReI). The d0/d1 transition in tetrathiometalates
Di- and trinuclear complexes with sulfide-bridged rhenium in very different oxidation states (ReIReVII, ReIReVIReI, ReIReVIIReI). The d0/d1 transition in tetrathiometalates
复制标题
具有不同氧化态的硫桥铼的二核和三核配合物（ReIReVII、ReIReVIReI、ReIReVIIReI）。
DOI：
10.1021/ic00066a036
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发表时间：
1993
影响因子：
4.6
通讯作者：
J. Fiedler
中科院分区：
文献类型：
--
作者：
R. Schaefer;Wolfang Kaim;J. Fiedler
结果化合物(NEt4)(I)和(NEt4)(II)的分析表征如实验部分和表I中所总结的。图1显示了电子吸收光谱。两种配合物都还原成双阴离子；然而，紫外/可见光和红外光谱电化学表明，对称性较低的络合物I-在第一次单电子还原后在约1分钟的时间尺度上缓慢分解。发现第二个还原步骤对于 I- 和 II- 都是不可逆的。通过紫外/可见光、红外和 EPR 光谱电化学研究了持久还原形式 II2-。即使在冷却至 3 K 后，在 EPR 毛细管中的 0.1 M Bu4NC1G4 乙腈、丙酮或 1, 2-二氯乙烷溶液中还原 II- 也不会产生信号。II2- 的 UV/vis 光谱显示与 II- 的吸收带相比略有移动；红外振动光谱显示 II-（表 I）还原时发生类似的微小变化。
ResultsThe compounds (NEt4)(I) and (NEt4)(II) were characterized analytically as summarized in the Experimental Section and in Table I. Figure 1 shows theelectronic absorption spectra. Both complexes undergo reduction to a dianion; however, U V/vis and IR spectroelectrochemistry showed that the less sym-metrical complex I-is slowly decomposing after the first one-electron reduction on the time scale of about 1 min. The second reduction steps were found irreversible for both I-and II-. The persistent reduced form II2-was studied by UV/vis, IR, and EPR spectroelectrochemistry. Reduction of II-in 0.1 M Bu4NC1G4 solutions of acetonitrile, acetone, or 1, 2-dichloroethane in an EPR capillary did not produce a signal, even after cooling to 3 K. The UV/vis spectrum of II2-shows slightly shifted absorption bands in relation to those of II-; IR vibrational spectra show similarly small changes on reduction of II-(Table I).