A complete series of tricarbonylhalidorhenium(I) complexes (abpy)Re(CO)3(Hal), Hal = F, Cl, Br, I;: abpy = 2,2′-azobispyridine:: Structures, spectroelectrochemistry and EPR of reduced forms
A complete series of tricarbonylhalidorhenium(I) complexes (abpy)Re(CO)3(Hal), Hal = F, Cl, Br, I;: abpy = 2,2′-azobispyridine:: Structures, spectroelectrochemistry and EPR of reduced forms
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DOI：
10.1016/j.jorganchem.2004.06.047
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发表时间：
2004-09-22
影响因子：
2.3
通讯作者：
Kaim, W
中科院分区：
文献类型：
--
作者：
Frantz, S;Fiedler, J;Kaim, W
以（abpy）Re(CO)(3)(Hal), abpy = 2,2′-偶氮双吡啶为例，首次系统地研究了一整套三羰基卤鎓(I)配合物（Hal = F, Cl, Br， I）。氯化物、溴化物和碘化物类似物的晶体结构现在是可用的，显示出abpy配体按此顺序增加平面化。还原态[(abpy)Re(CO)(3)(Hal)]的循环伏安、EPR、IR和UV/Vis光谱电化学研究。-)说明这四种卤化物配合物的性质只是部分不同。[(abpy)Re(CO)(3)F]（）的偏差最大。-)，其特点是电化学电位范围最广，但化学不稳定性最显著。在EPR光谱中，氟化物表现出最高的各向同性g值（2.0085）和最低的铼耦合常数，其量级与可探测到的F-19超细分裂相同（2 mT）。(C) 2004 Elsevier B.V.版权所有
For the first time a complete set of tricarbonylhalidorhenium(I) complexes (Hal = F, Cl, Br, I) has been studied in a systematical fashion by example of (abpy)Re(CO)(3)(Hal), abpy = 2,2'-azobispyridine. Crystal structures of chloride, bromide and iodide analogues are now available, showing increasing planarization of the abpy ligand in that order. Cyclic voltammetry, EPR, IR and UV/Vis spectroelectrochemistry of the reduced forms [(abpy)Re(CO)(3)(Hal)](.-) illustrate that the four halide complexes differ only partially in their properties. The strongest deviations are observed for [(abpy)Re(CO)(3)F](.-) which is distinguished by the widest electrochemical potential range but most pronounced chemical lability. In the EPR spectrum the fluoride exhibits the highest isotropic g value (2.0085) and the lowest rhenium coupling constant, which is of the same magnitude (2 mT) as the detectable F-19 hyperfine splitting. (C) 2004 Elsevier B.V. All rights reserved.