Iridium bis(phosphinite) p-XPCP pincer complexes:: Highly active catalysts for the transfer dehydrogenation of alkanes

被引：364

作者：

Göttker-Schnetmann, I ^{[1
]}

White, P ^{[1
]}

Brookhart, M ^{[1
]}

机构：

[1] Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 06期

关键词：

D O I：

10.1021/ja0385235

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A series of new bis(phosphinite) p-XPCPIrHCl pincer complexes {[PCP = eta(3)-5-X-C6H2[OP(tBU)(2)](2)-1,3], X = MeO (4a), Me (4b), H (4c), F (4d), C6F5 (4e), and Ar-F [=3,5-bis (trifluoromethyl)phenyl] (4f)} have been synthesized. Treatment of compounds 4a-f with NatOBu in cyclooctane (COA)/tert-butylethylene (TBE) mixtures generates species with unprecedented catalytic activity for the catalyzed transfer dehydrogenation of COA with TBE as acceptor to form cyclooctene (COE) and tert-butylethane (TBA). With substrate: precatalyst ratios of 3030COA:3030TBE:1p-XPCPIrHCl (4):1.1NaOtBu, turnover numbers (TONS) between 1400 and 2200 (up to 72% conversion in TBE) and initial turnover frequencies (TOFs) between 1.6 and 2.4 s(-1) have been observed at 200degreesC.

引用

页码：1804 / 1811

页数：8

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