期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 54, 期 38, 页码 11283-11288出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201504863
关键词
carbonyl homologues; crystal structures; DFT calculations; lead; rhodium clusters
资金
- Deutsche Forschungsgemeinschaft (DFG) [SPP 1415]
- Friedrich-Ebert-Stiftung
- Studienstiftung des deutschen Volkes
Reactions of [K(18-crown-6)](2)[Pb2Se3] and [K-([ 2.2.2] crypt)](2)[Pb2Se3] with [Rh(PPh3)(3)Cl] in en (ethane-1,2-diamine) afforded ionic compounds with [Rh-3(PPh3)(6)(mu(3)-Se)(2)](-) and [Rh-3(CN)(2)(PPh3)(4)(mu(3)-Se)(2)(mu-PbSe)](3-) anions, respectively. The latter contains a PbSe ligand, a rather uncommon homologue of CO that acts as a m-bridge between two Rh atoms. Quantum chemical calculations yield a significantly higher bond energy for PbSe than for CO, since the size of the ligand orbitals better matches the comparably rigid Rh-Se- Rh angles and the resulting Rh...Rh distance. To rationalize the bent coordination of the ligand, orbitals with significant ligand contributions and their dependence on the bonding angle were investigated in detail.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据