Cyclometalation of Anthyridine-Based Ligands with Dirhodium Acetates: Structure and Catalytic Activity

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• 作者：Da-wei Huang ; Ying-Hao Lo ; Yi-Hung Liu ; Shie-Ming Peng ; Shiuh-Tzung Liu
• 刊名：Organometallics
• 出版年：2013
• 出版时间：July 22, 2013
• 年：2013
• 卷：32
• 期：14
• 页码：4009-4015
• 全文大小：363K
• 年卷期：v.32,no.14(July 22, 2013)
• ISSN：1520-6041

文摘

Coordination of 2,8-Ar₂-5-phenylanthyridines (Ar = 2-thienyl, 1a; Ar = 2-ClC₆H₄鈥? 1b) with dirhodium tetraacetate yielded the cyclometalated complexes [Rh₂(OAc)₃(metalated-1a)] (3a) and [Rh₂(OAc)₃(metalated-1b)] (3b), respectively. Under acidic conditions, cleavage of the Rh鈥揅 bond in 3a,b took place to give the corresponding coordination complexes 4a,b. Treatment of 3a,b with PPh₃ led to the phosphine-cyclometalated species [Rh₂(OAc)₂{P,C-(C₆H₄)PPh₂}(metalated-1a)] (5a) and [Rh₂(OAc)₂{P,C-(C₆H₄)PPh₂}(metalated-1b)] (5b), respectively. These new dirhodium complexes have been structurally characterized by NMR spectroscopy, and some representative compounds were also analyzed by X-ray methods. The use of these newly prepared dirhodium complexes as catalysts for the allylic oxidation of cyclohexenes was investigated.