Oxidative addition of water by an iridium PCP pincer complex:: Catalytic dehydrogenation of alkanes by IrH(OH){C6H3-2,6-(CH2PBut2)2}

被引:127
作者
Morales-Morales, D [1 ]
Lee, DW [1 ]
Wang, ZH [1 ]
Jensen, CM [1 ]
机构
[1] Univ Hawaii, Dept Chem, Honolulu, HI 96822 USA
关键词
D O I
10.1021/om000940s
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The dehydrogenation of IrH2{C6H3-2,6-(CH2PBu2t)(2)} (1) by tert-butylethylene followed by reaction with an excess of water leads to the isolation of IrH(OH){C6H3-2,6-(CH2PBu2t)(2)} (2) in nearly quantitative yield. The hydride hydroxo complex has been characterized by multinuclear NMR spectroscopy as well as a single-crystal X-ray structure determination. An isotopic labeling study with D2O indicates that 2 arises from the oxidative addition of water to the intermediate 14-electron complex Ir{C6H3-2,6-(CH2PBu2t)(2)}. The title complex is an efficient catalyst for the transfer dehydrogenation of cyclooctane to cyclooctene but shows no catalytic activity for the hydroxylation of the alkane by water. The conversion of 1 to 2 can be reversed by placing a solution of 2 under 1 atm of H-2 at 25 degreesC.
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收藏
页码:1144 / 1147
页数:4
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