Bicyclic phosphines as ligands for cobalt-catalysed hydroformylation

被引：42

作者：

Crause, C ^{[1
]}

Bennie, L ^{[1
]}

Damoense, L ^{[1
]}

Dwyer, CL ^{[1
]}

Grove, C ^{[1
]}

Grimmer, N ^{[1
]}

van Rensburg, WJ ^{[1
]}

Kirk, MM ^{[1
]}

Mokheseng, KM ^{[1
]}

Otto, S ^{[1
]}

Steynberg, PJ ^{[1
]}

机构：

[1] Sasol Technol R&D, ZA-1947 Sasolburg, South Africa

来源：

DALTON TRANSACTIONS | 2003年 / 10期

关键词：

D O I：

10.1039/b210650g

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A range of tertiary phosphine ligands derived from (R)-(+)-limonene was studied by HP-P-31 NMR, HP-IR, batch autoclave reactions and molecular modelling during the hydroformylation of 1-dodecene using a cobalt catalyst system and a metal : ligand ratio of 1:2. The phosphorus atom was incorporated in a limonene bicycle where the third substituent was systematically varied, Lim-R (R=(CH2)(17)CH3, (CH2)(9)CH3, (CH2)(4)CH3, (CH2)(3)CH3, (CH2)(3)C6H5, (CH2)(3)CN, (CH2)(3)OCH2C6H5, (CH2)(2)OCH2CH3). The activity and selectivity was, to a large extent, governed by the equilibria between the modified and unmodified cobalt catalytic species in the reaction. Linearity ranged from 54 to 71% with Lim-(CH2)(3)CN yielding the most branched product and Lim-(CH2)(4)CH3 the most linear product. The n:iso ratio (ratio of linear to 2-methyl branched alcohol) also followed the same trend with a ratio of 2.6 for Lim-(CH2)(3)CN and 4.9 for Lim-(CH2)(4)CH3. The rate decreased as the linearity increased with pseudo k values of 0.5 to 1.1. Hydrogenation of the alkene varied within a narrow band from 5-6%.

引用

页码：2036 / 2042

页数：7

共 27 条

[1]

[Anonymous], [No title captured], Patent No. [US 3420898, 3420898]

[2] PROGRESS IN HYDROFORMYLATION AND CARBONYLATION [J].