Computational and Experimental Investigation of Alkene Hydrogenation by a Pincer-Type [P2Si]Rh Complex: Alkane Release via Competitive σ-Bond Metathesis and Reductive Elimination

被引：13

作者：

Whited, Matthew T. ^{[1
]}

Trenerry, Michael J. ^{[1
]}

DeMeulenaere, Kaitlyn E. ^{[1
]}

Taylor, Buck L. H. ^{[1
,2
]}

机构：

[1] Carleton Coll, Dept Chem, Northfield, MN 55057 USA

[2] Univ Portland, Dept Chem, Portland, OR 97203 USA

来源：

ORGANOMETALLICS | 2019年 / 38卷 / 07期

基金：

美国国家科学基金会;

关键词：

DIHYDROGEN COMPLEXES; RHODIUM; IRIDIUM; LIGAND; CO2; ACTIVATION; REACTIVITY; MECHANISM; PSIP;

D O I：

10.1021/acs.organomet.8b00922

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A combined experimental and computational approach has been utilized to elucidate the mechanism of alkene hydrogenation by pincer-type [P2Si]Rh catalysts. Although [P2Si]Rh interacts with H-2 to afford a dihydrogen sigma-complex rather than a dihydride (seemingly an indication of facile reductive elimination from Rh(III)), alkane release occurs by competitive sigma-bond metathesis (bimolecular) and reductive elimination (unimolecular) pathways. This unusual behavior is attributed to the strong trans influence of the silyl donor.

引用

页码：1493 / 1501

页数：9

共 39 条

[1] FACIAL (METHYL)(HYDRIDO)(SILYL) COMPLEXES OF IRIDIUM - SYNTHESIS, X-RAY STRUCTURES, AND REDUCTIVE ELIMINATION-REACTIONS - FACILE FORMATION OF SILAMETALLACYCLES BY METALATION OF SILYL LIGANDS [J].

AIZENBERG, M ;

MILSTEIN, D .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (24) :6456-6464

[2]

[Anonymous], HDB HOMOGENEOUS HYDR

[3]

[Anonymous], 2007, The Handbook of Homogeneous Hydrogenation

[4] INTERCEPTION AND CHARACTERIZATION OF A HYDRIDOALKYLRHODIUM INTERMEDIATE IN A HOMOGENEOUS CATALYTIC-HYDROGENATION REACTION [J].

CHAN, ASC ;

HALPERN, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (02) :838-840

[5]

Coperet C, 2007, HYDROGENATION WITH E, V1, P111

[6] Reactions of Hydrosilanes with Transition Metal Complexes [J].

Corey, Joyce Y. .

CHEMICAL REVIEWS, 2016, 116 (19) :11291-11435

[7]

Crabtree R. H, 2007, HDB HOMOGENEOUS HYDR, V1, P31

[8] Dihydrogen Complexation [J].

Crabtree, Robert H. .

CHEMICAL REVIEWS, 2016, 116 (15) :8750-8769

[9]

Felgdus S., 2002, COMPUTATIONAL MODELI, V25, P107

[10] Dihydrogen Complexes of Iridium and Rhodium [J].

Findlater, Michael ;

Schultz, Katherine M. ;

Bernskoetter, Wesley H. ;

Cartwright-Sykes, Alison ;

Heinekey, D. Michael ;

Brookhart, Maurice .

INORGANIC CHEMISTRY, 2012, 51 (08) :4672-4678

← 1 2 3 4 →