標題: Journey from Mo-Mo Quadruple Bonds to Quintuple Bonds
作者: Tsai, Yi-Chou
Chen, Hong-Zhang
Chang, Chie-Chieh
Yu, Jen-Shiang K.
Lee, Gene-Hsiang
Wang, Yu
Kuo, Ting-Shen
生物科技學系
生物資訊及系統生物研究所
Department of Biological Science and Technology
Institude of Bioinformatics and Systems Biology
公開日期: 9-Sep-2009
摘要: Heating K(4)Mo(2)Cl(8) and 2 equiv of Li[RC(NDipp)(2)] (R = H, Ph; Dipp = 2,6-i-Pr(2)C(6)H(3)) in tetrahydrofuran (THF) at 60 degrees C gives two paddlewheel type quadruply bonded dimolybdenum complexes, Mo(2)(mu-Cl)[Cl(2)Li(OEt(2))][mu-eta(2)-RC(N-2,6-i-Pr(2)C(6)H(3))(2)](2) (R = H (1), Ph (2)). The Mo-Mo bond lengths of 1 and 2 are 2.0875(4) and 2.0756(8) angstrom, respectively, indicating typical Mo-Mo quadruple bonds. Reduction of 1 and 2 by two electrons results in the isolation of their corresponding Mo-Mo quintuple bonded complexes, Mo(2)[mu-eta(2)-RC(N-2,6-i-Pr(2)C(6)H(3))(2)](2) (R = H (3), Ph (4)), and the Mo-Mo bond lengths dramatically decrease to 2.0187(9) angstrom (3) and 2.0157(4) angstrom (4), a consequence of the formation of the second delta bond and representing the shortest metal-metal bonds beyond the first row elements. The Mo-Mo quintuple bonding characters are corroborated by DFT calculations at the level of BP86/def2-TZVP and BP86/def2-TZVPP.
URI: http://dx.doi.org/10.1021/ja905035f
http://hdl.handle.net/11536/6684
ISSN: 0002-7863
DOI: 10.1021/ja905035f
期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume: 131
Issue: 35
起始頁: 12534
結束頁: +
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