Intramolecular C–H Bond Activation in Bridged Dicyclopentadienyl Dimethyl Dinuclear Complexes
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- 作者：Bolin Zhu ; Xiaoting Hao ; Yunfei Chen
- 刊名：Organometallics
- 出版年：2014
- 出版时间：January 13, 2014
- 年：2014
- 卷：33
- 期：1
- 页码：240-248
- 全文大小：571K
- ISSN：1520-6041
文摘
Photolysis of the doubly bridged dicyclopentadienyl dimethyl dinuclear complexes [(畏5-C5H2R)2(SiMe2)2]M2(CO)4Me2 (M = Ru, R = H (2a), tBu (2b); M = Fe, R = H (2c)) in benzene yields the corresponding methylene-bridged complexes [(畏5-C5H2R)2(SiMe2)2]M2(CO)2(渭-CO)(渭-CH2) (3a鈥?b>c) and the M鈥揗-bonded complexes [(畏5-C5H2R)2(SiMe2)2]M2(CO)4 (1a鈥?b>c). Irradiation of the analogous diethyl complex [(畏5-C5H2R)2(SiMe2)2]Ru2(CO)4Et2 (4) affords only 1a. Unlike the case for the doubly bridged complexes, photolysis of the singly bridged dicyclopentadienyl dimethyl diruthenium complexes [(畏5-C5H4)2(EMe2)]Ru2(CO)4Me2 (E = C (5a); E = Si (5b)) in benzene yields the corresponding 鈥渢wisted鈥?ruthenium methyl complexes with a cyclopentadienyl鈥揜u 蟽 bond (畏5,畏5:畏1-C5H4(EMe2)C5H3)[Ru(CO)2][Ru(CO)2Me] (6a,b) and the similar phenyl complexes (畏5,畏5:畏1-C5H4(EMe2)C5H3)[Ru(CO)2][Ru(CO)2Ph] (7a,b), from reaction with the benzene solvent. Plausible mechanisms for the formation of the different types of products are proposed involving intramolecular C鈥揌 bond activation. The molecular structures of 2a,c, 3a,c, 4, 5a, 6a, and 7b, determined by X-ray diffraction, are also presented.