Synthesis, Structure, and Hydrothiolation Activity of Rhodium Pyrazolylborate Complexes

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• 作者：Lauren R. Fraser ; Jeffrey Bird ; Qiming Wu ; Changsheng Cao ; Brian O. Patrick ; Jennifer A. Love
• 刊名：Organometallics
• 出版年：2007
• 出版时间：November 5, 2007
• 年：2007
• 卷：26
• 期：23
• 页码：5602 - 5611
• 全文大小：243K
• 年卷期：v.26,no.23(November 5, 2007)
• ISSN：1520-6041

文摘

A series of rhodium pyrazolylborate complexes [Tp^RRh(PPh₃)₂] {Tp^R = HBR'₃, R' = 3,5-dimethylpyrazolyl (1), pyrazolyl (3), 3-phenylpyrazolyl (4), or 3-phenyl-5-methylpyrazolyl (5)} and [Bp^RRh(PPh₃)₂] {Bp^R = H₂BR'₂, R' = 3,5-dimethylpyrazolyl (2)} were prepared from [ClRh(PPh₃)₃] and KX(X = pyrazolylborate anion). Complexes 2-5 were characterized crystallographically. The solutionstructures of new complexes 4 and 5 were also examined by variable temperature NMR and IRspectroscopy. The catalytic activity of complexes 1-5 in alkyne hydrothiolation was then examined. Itwas found that disubstituted tris(pyrazolyl)borate complexes (1 and 5) give the best selectivity and yieldin alkyne hydrothiolation with aliphatic thiols.