Raman Spectroscopy of Three Average-Valence Dicopper Cryptates: Evidence for Copper-Copper Bonding

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• 作者：Ala Al-Obaidi ; Goran Baranovig src="http ; //pubs.acs.org/images/entities/ccaron.gif" border="0"> ; Joanne Coyle ; Colin G. Coates ; John J. McGarvey ; Vickie McKee ; and Jane Nelson
• 刊名：Inorganic Chemistry
• 出版年：1998
• 出版时间：July 13, 1998
• 年：1998
• 卷：37
• 期：14
• 页码：3567 - 3574
• 全文大小：146K
• 年卷期：v.37,no.14(July 13, 1998)
• ISSN：1520-510X

文摘

Comparison of the X-ray structures of two pairs of dicopper(I) and dicopper(1.5) cryptates provides evidence(over 0.5 Å contraction of the internuclear distance in one pair) for copper-copper bond formation. Althoughresonance Raman spectroscopy fails to identify a pure copper-copper stretching mode, because of extensivemixing of several low-frequency stretching and bending modes, isotopic substitution experiments indicate significantCu-Cu character in a band around 250 cm^-1. A normal coordinate analysis broadly supports the spectroscopicfindings. X-ray crystal structures are presented for the dicopper(1.5) complex Cu₂imBT(ClO₄)₃, C₁₈H₃₀Cl₃Cu₂N₈O₁₂,a = 9.140(4) Å, c = 30.35(3) Å, rhombohedral, R32, Z = 3, and the dicopper(I) Cu₂imbistrpn(ClO₄)₂, C₂₄H₄₂Cl₂Cu₂N₈O₈, a = 9.279(2) Å, c = 32.846(9) Å, rhombohedral, R32, Z = 3.