Dicopper Complexes with Anthyridine-Based Ligands: Coordination and Catalytic Activity

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• 作者：Da-wei Huang ; Yi-Hung Liu ; Shie-Ming Peng ; Shiuh-Tzung Liu
• 刊名：Organometallics
• 出版年：2016
• 出版时间：January 25, 2016
• 年：2016
• 卷：35
• 期：2
• 页码：151-158
• 全文大小：453K
• ISSN：1520-6041

文摘

Two new anthyridine-based ligands, 5-phenyl-2,8-bis(2-pyridinyl)-1,9,10-anthyridine (L₃) and 5-phenyl-2,8-bis(6′-bipyridinyl)-1,9,10-anthyridine (L₄), were designed for accommodation of dimetallic systems with the metal ions separated by ～5 ?. Complexation of Cu(ClO₄)₂ with L₃ and L₄ provided the corresponding dicopper complexes [{Cu₂(L₃)(H₂O)₄(CH₃CN)₂}(ClO₄)₄] (3) and [{Cu₂(L₄)(μ-ClO₄)₂}(PF₆)₂] (4), respectively. Both complexes were characterized by spectroscopic methods, and the detail structural features were further confirmed by X-ray crystallography. Structural analyses of 3 and 4 reveal the Cu···Cu distances in the complexes being 4.9612(7) and 5.013 (2) ?, respectively. Both complexes are active in the catalytic oxidation of benzyl alcohols into the corresponding aldehydes. Furthermore, complex 4 appears to be a good catalyst for the oxidative coupling of primary alcohols into the corresponding esters with the use of hydrogen peroxide as the oxidant in an aqueous medium. The possible cooperative interactions between the metal ions during the catalysis are discussed.