Metal-metal electronic coupling in syn and anti stereoisomers of mixed-valent (FeCp)2-, (RhL2)2-, and (FeCp)(RhL2)-as-indacenediide ions.
Metal-metal electronic coupling in syn and anti stereoisomers of mixed-valent (FeCp)2-, (RhL2)2-, and (FeCp)(RhL2)-as-indacenediide ions.
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混合价 (FeCp)2-、(RhL2)2- 和 (FeCp)(RhL2)- 作为二茚二离子离子的顺式和反式立体异构体中的金属-金属电子耦合。
DOI：
10.1002/chem.200700052
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发表时间：
2007
期刊：
影响因子：
--
通讯作者：
L. Crociani
中科院分区：
文献类型：
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作者：
S. Santi;L. Orian;Christian Durante;É. Bencze;Annalisa Bisello;Alessandro Donoli;A. Ceccon;F. Benetollo;L. Crociani
用光谱电化学和密度泛函理论研究了（FeCp）（2）-、（RhL（2））（2）-和（FeCp）（RhL（2））-（L（2）= 1，5-环辛烯（cod），L = CO）as-引达省二烯混合价离子的顺式和反式立体异构体的金属-金属电子耦合程度.金属单元相对于平面芳族配体的顺/反取向的效果表明电子转移通过桥而不是通过空间发生。金属的性质被发现是至关重要的：虽然同双金属二铁物种是局部价态捕获离子（II类），dirhodium类似物几乎是离域的混合价离子（边界和III类）。最后，尽管它们的氧化还原不对称性，即使在heterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloheterocycloh事实上，铁中心的氧化伴随着从铑到铁的电子转移和反应性17电子铑位点的形成。顺式和反式Fe-Rh as-indacenedide络合物是可被分类为临界II类/III类物质的杂环体系的罕见实例。
The extent of metal-metal electronic coupling was quantified for a series of syn and anti stereoisomers of (FeCp)(2)-, (RhL(2))(2)- and (FeCp)(RhL(2))- (L(2)=1,5-cyclooctadiene (cod), L=CO) as-indacenediide mixed-valent ions by spectroelectrochemical and DFT studies. The effect of the syn/anti orientation of the metal units with respect to the planar aromatic ligand indicates that electron transfer occurs through the bridge rather than through space. The nature of the metal was found to be crucial: while homobimetallic diiron species are localised valence-trapped ions (Class II), the dirhodium analogues are almost delocalised mixed-valent ions (borderline and Class III). Finally, despite their redox asymmetry, even in the heterobimetallic iron-rhodium as-indacenediide complexes, strong metal-metal coupling is present. In fact, oxidation of the iron centre is accompanied by electron transfer from rhodium to iron and formation of a reactive 17-electron rhodium site. syn and anti Fe-Rh as-indacenediide complexes are rare examples of heterobimetallic systems which can be classified as borderline Class II/Class III species.