Isomers of Cyclometalated Macrocycles Constructed through Olefinic C–H Activation
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- 作者：Long Zhang ; Hao Li ; Lin-Hong Weng ; Guo-Xin Jin
- 刊名：Organometallics
- 出版年：2014
- 出版时间：January 27, 2014
- 年：2014
- 卷：33
- 期：2
- 页码：587-593
- 全文大小：485K
- ISSN：1520-6041
文摘
A new series of dinuclear complexes [(Cp*M)2{(2-pyridyl)-C鈺怌-(2-pyridyl)}Cl2] (M = Rh (1a), Ir (1b)) and tetranuclear metallamacrocycles [{(Cp*M)2{(2-pyridyl)-C鈺怌-(2-pyridyl)}(pyrazine)}2](OTf)4 (M = Rh (2a), Ir (2b)), [{(Cp*M)2{(2-pyridyl)-C鈺怌-(2-pyridyl)}(bpy)}2](OTf)4 (M = Rh (3a), Ir (3b); bpy = 4,4鈥?bipyridine), and [{(Cp*M)2{(2-pyridyl)-C鈺怌-(2-pyridyl)}(bpe)}2](OTf)4 (M = Rh (4a), Ir (4b); 4,4鈥?bpe = trans-1,2-bis(4-pyridyl)ethylene) were constructed stepwise through double-site C鈥揌 activation on the olefinic C鈺怌 bond of 1,2-bis(2-pyridyl)ethylene. Isomers were observed in both the dinuclear species and tetranuclear macrocyclic complexes and were confirmed by single-crystal X-ray diffraction. The molecular structures of 1a鈥?b>c, (R,R)-(S,S)-3b, (R,R)-(S,S)-4a, (R,R)-(R,R)-/(S,S)-(S,S)-4a, and (R,R)-(S,S)-4b were characterized by single-crystal X-ray crystallography. All complexes were fully characterized by 1H NMR spectroscopy, ESI-MS, and elemental analysis.