Double Activation of the Geminal Carbon-Hydrogen Bonds in 1,3-Butadiene by a Diiridium Complex
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- 作者：Dusan Ristic-Petrovic ; Jeffrey R. Torkelson ; Robert W. Hilts ; Robert McDonald ; and Martin Cowie
- 刊名：Organometallics
- 出版年：2000
- 出版时间：October 30, 2000
- 年：2000
- 卷：19
- 期：22
- 页码：4432 - 4434
- 全文大小：52K
- 年卷期：v.19,no.22(October 30, 2000)
- ISSN：1520-6041
文摘
The binuclear complex [Ir2(CH3)(CO)2(dppm)2][CF3SO3] (1) (dppm = Ph2PCH2PPh2) reacts with 1,3-butadiene at ambient temperature over a 48 h period togive the vinylvinylidene-bridged product [Ir2(CH3)(H)(CO)2(
-H)(-CC(H)C(H)CH2)(dppm)2][CF3SO3] (2). At-55 
C the same reactants yield the 1,3-butadieneadduct [Ir2(CH3)(CO)2(-
2:2-H2C=C(H)C(H)=CH2)(dppm)2][CF3SO3] (3), in which the diolefin binds in ans-trans geometry on one face of the complex. A proposalis advanced rationalizing the conversion of 3 to 2 uponwarming.
-H)(-CC(H)C(H)CH2)(dppm)2][CF3SO3] (2). At-55 C the same reactants yield the 1,3-butadieneadduct [Ir2(CH3)(CO)2(-2:2-H2C=C(H)C(H)=CH2)(dppm)2][CF3SO3] (3), in which the diolefin binds in ans-trans geometry on one face of the complex. A proposalis advanced rationalizing the conversion of 3 to 2 uponwarming.