In:
Zeitschrift für Naturforschung B, Walter de Gruyter GmbH, Vol. 42, No. 12 ( 1987-12-1), p. 1527-1536
Abstract:
PhP(CH 2 C 4 H 7 O 2 ) 2 (1) and [-CH 2 (Ph)P~D] 2 (3a-c) [D = CH 2 C 4 H 7 0 2 (a), CH 2 C 4 H 7 O (b). CH 2 CH 2 OCH 3 (c)] are obtained by reaction of Li 2 PPh and Na(Ph)P~D with ClCH 2 C 4 H 7 O 2 and C1CH 2 CH 2 Cl, respectively. 1 and 3a, b give rise to high selectivities and conversions in the cobalt catalyzed hydrocarbonylation of methanol to acetaldehyde. Model complexes of cobalt which are of importance in the catalytic cycle are synthesized. Complexes of the type X 2 Co(Ph 2 P~D) 2 (6az, 6bx-bz, 6cx-cz), especially those with X = I, obtained from CoX 2 [X = Cl (x), Br (y), I (z)] and the ether phosphanes Ph 2 P~D (5a-c), are regarded as precursors of the catalytically active species. With K[HB(sec-C 4 H 9 ) 3 ] they are reduced to the cobalt(I) complexes XCo(Ph 2 P~D)(Ph 2 P~D) (7az, 7bx-bz, 7cx-cz). Trapping reactions with CO, PPh 3 or 5b, c lead to the compounds XCo(CO) 2 (Ph 2 P~D) 2 (8az, 8bx-bz, 8cx-cz), XCoPPh 3 (Ph 2 P~D) 2 (9bx-bz). and XCo(Ph 2 P~D) 3 (10bz, cz), respectively, with cleavage of a Co-O bond. The reduction of X 2 Co(PPh 3 ) 2 (11x, z) with K[HB(sec-C 4 H 9 ) 3 ] represents a simple method for the preparation of the complexes XCo(CO) 2 (PPh 3 ) 2 (13x, z) which are formed from the intermediates XCo(PPh 3 ) 2 · THF (12x, z) in the presence of CO.
Type of Medium:
Online Resource
ISSN:
1865-7117
,
0932-0776
DOI:
10.1515/znb-1987-1207
Language:
English
Publisher:
Walter de Gruyter GmbH
Publication Date:
1987
detail.hit.zdb_id:
2078109-X
detail.hit.zdb_id:
124635-5
Permalink