Journey from Mo-Mo quadruple bonds to quintuple bonds

Yi Chou Tsai*, Hong Zhang Chen, Chie Chieh Chang, Jen-Shiang K. Yu, Gene Hsiang Lee, Yu Wang, Ting Shen Kuo

*Corresponding author for this work

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77 Scopus citations

Abstract

(Chemical Equation Presented) Heating K4Mo2Cl 8 and 2 equiv of Li[RC(NDipp)2] (R = H, Ph; Dipp = 2,6-i-Pr2C6H3) in tetrahydrofuran (THF) at 60°C gives two paddlewheel type quadruply bonded dimolybdenum complexes, Mo2(μ -Cl)[Cl2Li(OEt2)][μ- η2-RC(N-2,6-i-Pr2C6H3) 2]2 (R = H (1), Ph (2)). The Mo-Mo bond lengths of 1 and 2 are 2.0875(4) and 2.0756(8) Å, 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, Mo2[μ- η2-RC(N-2,6-i-Pr2C6H3) 2]2 (R = H (3), Ph (4)), and the Mo-Mo bond lengths dramatically decrease to 2.0187(9) Å (3) and 2.0157(4) Å (4), a consequence of the formation of the second δ 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.

Original languageEnglish
Pages (from-to)12534-12535
Number of pages2
JournalJournal of the American Chemical Society
Volume131
Issue number35
DOIs
StatePublished - 9 Sep 2009

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    Tsai, Y. C., Chen, H. Z., Chang, C. C., Yu, J-S. K., Lee, G. H., Wang, Y., & Kuo, T. S. (2009). Journey from Mo-Mo quadruple bonds to quintuple bonds. Journal of the American Chemical Society, 131(35), 12534-12535. https://doi.org/10.1021/ja905035f