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

被引：373

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

共 55 条

[1] SELECTIVE INTERMOLECULAR CARBON-HYDROGEN BOND ACTIVATION BY SYNTHETIC METAL-COMPLEXES IN HOMOGENEOUS SOLUTION [J].

ARNDTSEN, BA ;

BERGMAN, RG ;

MOBLEY, TA ;

PETERSON, TH .

ACCOUNTS OF CHEMICAL RESEARCH, 1995, 28 (03) :154-162

[2]

BAUDRY MJ, 1984, ORGANOMETALLICS, V3, P816

[3]

BAUDRY MJ, 1983, J CHEM SOC CHEM COMM, P788

[4] Palladium bis(phosphinite) 'PCP'-pincer complexes and their application as catalysts in the Suzuki reaction [J].

Bedford, RB ;

Draper, SM ;

Scully, PN ;

Welch, SL .

NEW JOURNAL OF CHEMISTRY, 2000, 24 (10) :745-747

[5] Catalytic alkane dehydrogenation by IrClH2(PPr3i)(2): Evidence for an alkane associative mechanism [J].

Belli, J ;

Jensen, CM .

ORGANOMETALLICS, 1996, 15 (06) :1532-1534

[6] Boron trichloride/tetra-n-butylammonium iodide:: A mild, selective combination reagent for the cleavage of primary alkyl aryl ethers [J].

Brooks, PR ;

Wirtz, MC ;

Vetelino, MG ;

Rescek, DM ;

Woodworth, GF ;

Morgan, BP ;

Coe, JW .

JOURNAL OF ORGANIC CHEMISTRY, 1999, 64 (26) :9719-9721

[7] SELECTIVE CATALYTIC DEHYDROGENATION OF ALKANES TO ALKENES [J].

BURK, MJ ;

CRABTREE, RH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (26) :8025-8032

[8] Alkane C-H activation and functionalization with homogeneous transition metal catalysts: a century of progress-a new millennium in prospect [J].

Crabtree, RH .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2001, (17) :2437-2450

[9] IRIDIUM COMPLEXES IN ALKANE DEHYDROGENATION [J].

CRABTREE, RH ;

MIHELCIC, JM ;

QUIRK, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (26) :7738-7740

[10] Synthesis of 1,2-diheteroatom-substituted alkenes via rhodium-catalyzed intramolecular hydrogen transfer [J].

Diaz-Requejo, MM ;

DiSalvo, D ;

Brookhart, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (08) :2038-2039

← 1 2 3 4 5 6 →