Substitution and Isomerization of Asymmetric β-Diketonato Rhodium(I) Complexes: A Crystallographic and Computational Study

被引：25

作者：

Hopmann, Kathrin H. ^{[1
,2
]}

Stuurman, Nomampondomise F. ^{[3
]}

Muller, Alfred ^{[4
]}

Conradie, Jeanet ^{[1
,2
,3
]}

机构：

[1] Univ Tromso, Ctr Theoret & Computat Chem, N-9037 Tromso, Norway

[2] Univ Tromso, Dept Chem, N-9037 Tromso, Norway

[3] Univ Orange Free State, Dept Chem, ZA-9300 Bloemfontein, South Africa

[4] Univ Johannesburg, Dept Chem, ZA-2006 Johannesburg, South Africa

来源：

ORGANOMETALLICS | 2010年 / 29卷 / 11期

基金：

新加坡国家研究基金会;

关键词：

IODOMETHANE OXIDATIVE ADDITION; EFFECTIVE CORE POTENTIALS; CRYSTAL-STRUCTURE; TRANS ISOMERIZATION; MONOCARBONYLPHOSPHINE COMPLEXES; MOLECULAR CALCULATIONS; IR SPECTROPHOTOMETRY; REACTION-MECHANISM; NMR-SPECTROSCOPY; UTILIZING UV/VIS;

D O I：

10.1021/om1000138

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Ligand substitution of PPh3 for CO in the asymmetric square-planar beta-diketonato complex [Rh(PhCOCHCOCH2CH3)(CO)(2)] leads to formation of the monosubstituted [Rh(PhCOCHCOCH2CH3)(CO)(PPh3)] product. Two geometrical product isomers are possible, which unexpectedly crystallize in the same crystal lattice. DFT calculations of the substitution reaction support a twostep mechanism, involving temporary dissociation of a beta-diketonato ligand and formation of a square-planar intermediate. Analysis of the mechanisms involved in product isomerization suggests several noncatalyzed and solvent-assisted interconversion pathways.

引用

页码：2446 / 2458

页数：13

共 50 条

[31] A SPECTROSCOPIC STUDY OF HALOCARBONYL COMPLEXES OF RHODIUM(I) AND RHODIUM(III)
HEATON, BT
JACOB, C
MOFFET, S
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1993, 462 (1-2) : 347 - 352
[32] Iodomethane oxidative addition to β-diketonatobis(triphenylphosphite)rhodium(I) complexes: A synthetic, kinetic and computational study
Conradie, Marrigje M.
Erasmus, Johannes J. C.
Conradie, Jeanet
POLYHEDRON, 2011, 30 (13) : 2345 - 2353
[33] ASYMMETRIC HOMOGENEOUS HYDROGENATION OF OLEFINS CATALYZED BY ALKYLPHOSPHINE COMPLEXES OF RHODIUM(I)
CULLEN, WR
WOOLLINS, JD
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1982, 60 (14): : 1793 - 1799
[34] STUDY OF HYDROGENATION AND ISOMERIZATION OF ALLYLBENZENE CATALYZED BY CHLORODIMETHYLSULFOXIDE COMPLEXES OF PALLADIUM AND RHODIUM
NAZAROVA, NM
KOPYTTSE.YA
VARAVA, TI
FREIDLIN, LK
IZVESTIYA AKADEMII NAUK SSSR-SERIYA KHIMICHESKAYA, 1972, (06): : 1422 - &
[35] Asymmetric hydroformylation of vinyl acetate with BINAP-rhodium(I) complexes
Hoegaerts, D
Jacobs, PA
TETRAHEDRON-ASYMMETRY, 1999, 10 (15) : 3039 - 3043
[36] KINETICS OF THE SUBSTITUTION OF BETA-DIKETONES IN BETA-DIKETONATO(1,5-CYCLOOCTADIENE)RHODIUM(I) COMPLEXES BY BENZOYL-1,1,1-TRIFLUOROACETONE
POTGIETER, JH
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1989, 366 (03) : 369 - 375
[37] Mechanism of Asymmetric Hydrogenation of β-Dehydroamino Acids Catalyzed by Rhodium Complexes: Large-Scale Experimental and Computational Study
Gridnev, Ilya D.
Liu, Yuanyuan
Imamoto, Tsuneo
ACS CATALYSIS, 2014, 4 (01): : 203 - 219
[38] BIS[(R)-(+)-BINAP]RHODIUM(I) PERCHLORATE, A HIGHLY EFFICIENT CATALYST FOR THE ASYMMETRIC ISOMERIZATION OF ALLYLAMINES
TANI, K
YAMAGATA, T
TATSUNO, Y
YAMAGATA, Y
TOMITA, K
AKUTAGAWA, S
KUMOBAYASHI, H
OTSUKA, S
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1985, 24 (03): : 217 - 219
[39] Rhodium(I)-Catalyzed Domino Asymmetric Ring Opening/Enantioselective Isomerization of Oxabicyclic Alkenes with Water
Tsui, Gavin C.
Lautens, Mark
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (22) : 5400 - 5404
[40] INTRAMOLECULAR LIGAND SUBSTITUTION IN SQUARE-PLANAR RHODIUM(I) CATIONIC COMPLEXES
YUAN, GQ
WANG, DG
LIU, SH
CHEN, RY
KEXUE TONGBAO, 1984, 29 (08): : 1053 - 1057

← 1 2 3 4 5 →