Diversity of the Structures in a Distannene Complex and its Reduction to Generate a Six-Membered Ti2Sn4 Ring Complex

被引:27
作者
Kuwabara, Takuya [1 ]
Guo, Jing Dong [2 ]
Nagase, Shigeru [2 ]
Saito, Masaichi [1 ]
机构
[1] Saitama Univ, Grad Sch Sci & Engn, Dept Chem, Sakura Ku, Saitama 3388570, Japan
[2] Kyoto Univ, Fukui Inst Fundamental Chem, Sakyo Ku, Kyoto 6068103, Japan
关键词
metallacycles; multiple bonds; sandwich complexes; tin; titanium; AROMATICITY; ZIRCONOCENE; REACTIVITY; CHEMISTRY; GERMANIUM; PLATINUM; ADDUCTS; SILICON; ANALOG; ROUTE;
D O I
10.1002/anie.201308565
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In contrast to olefin complexes, their congeners of heavier elements display various coordination modes, and their complexes may be present as bis(metallylene) complexes, with side-on coordination, as metallacyclopropanes, or as complexes. In the course of our studies on the reactivity of dilithiostannoles towards transition-metal reagents, three-membered TiSn2 and six-membered Ti2Sn4 ring complexes were obtained. According to its geometric parameters, NMR analysis, and theoretical calculations, the TiSn2 complex cannot be categorized into any of these previously described bonding modes. Therefore, a novel resonance structure has been proposed for a complex that has a delocalized sigma-orbital over the TiSn2 ring to understand its electronic structure. The mechanism for the formation of the Ti2Sn4 ring complex and its EPR spectrum are also discussed.
引用
收藏
页码:434 / 438
页数:5
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