LIGAND-INDUCED FRAGMENTATION OF METHYLNICKEL PHENOLATES CONTAINING A 2-ALDEHYDE FUNCTION - STRUCTURE OF (3-TERT-BUTYL-5-METHYL-2-OXOBENZOYL)-TRIS(TRIMETHYLPHOSPHINE) NICKEL

被引：22

作者：

KLEIN, HF ^{[1
]}

BICKELHAUPT, A ^{[1
]}

HAMMERSCHMITT, B ^{[1
]}

机构：

[1] UNIV GH PADERBORN,D-33095 PADERBORN,GERMANY

来源：

ORGANOMETALLICS | 1994年 / 13卷 / 08期

关键词：

D O I：

10.1021/om00020a009

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

O-bridging salicylaldehyde derivatives in dimeric methylnickel compounds NiMe(OR)(PMe3) showing equilibria of cis and trans forms (OR = 2-oxobenzaldehyde (1), 3-tert-butyl-5-methyl-2-oxobenzaldehyde (2), 3,5-di-tert-butyl-2-oxobenzaldehyde (3), 2-oxonaphthaldehyde (4)) spontaneously undergo, upon addition of trimethylphosphine, a fragmentation reaction forming 2-oxobenzoyl-C,O chelating ligands in 18-electron mononuclear complexes Ni(OC=O)(PMe3)3 (OC=O = 2-oxobenzoYl (5), 3-tert-butyl-5-methyl-2-oxobenzoyl (6), 3,5-di-tert-butyl-2-oxobenzoYl (7), 2-oxonaphthoyl (8)). The molecular structure of 6 contains pentacoordinate nickel with a chelate bite angle C-Ni-O = 85.5(1)-degrees. Dissociation of phosphine ligands in 5 gives Ni(OC=O)(PMe3)2 (9) and [Ni(OC)(PMe3)]2 (10), but no mobilization of carbonyl ligands could be observed in the presence of Ni(PMe3)4 as CO acceptor.

引用

页码：2944 / 2950

页数：7

共 18 条

[1] BINUCLEAR COMPLEXES OF NICKEL WITH THE BRIDGING ORTHO-CH2C6H4 LIGAND - SYNTHESIS AND REACTIONS - X-RAY CRYSTAL-STRUCTURE OF TRANS-(ME3P)2BRNI(C(O)C6H4-ORTHO-CH2)NIBR(PME3), A COMPLEX CONTAINING A BRIDGING MU-2-ETA-1-ETA-1-AROYL LIGAND [J].