Trimethylphosphine complexes of diorganonickel(IV) moieties

被引：48

作者：

Klein, HF ^{[1
]}

Bickelhaupt, A ^{[1
]}

Lemke, M ^{[1
]}

Sun, HJ ^{[1
]}

Brand, A ^{[1
]}

Jung, T ^{[1
]}

Rohr, C ^{[1
]}

Florke, U ^{[1
]}

Haupt, HJ ^{[1
]}

机构：

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

来源：

ORGANOMETALLICS | 1997年 / 16卷 / 04期

关键词：

D O I：

10.1021/om960436g

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

When coordinated to 8-oxobenzoyl-C,O chelating ligands (OC=O) (= 3-tert-butyl-5-methylphenyl, 3,5-di-tert-butylphenyl, 3-methoxyphenyl, 3,4-benzocyclohexenyl, cyclohexenyl), 18 electron nickel(II) complexes Ni(OC=O)(PMe(3))(3) (1-5) oxidatively add iodomethane affording thermally labile Ni-IV compounds trans-mer-Ni(Me)I(OC=O)(PMe(3))(2) (6-10) or react with iodine in a ligand dismutation reaction to form stable molecules of trans-Ni(OC=O)(2)(PMe(3))(2) (21-25), which contain cisoidal acylphenolato chelate rings. Acylphenolato compounds 1-5 react with larger electrophiles [C2H5I, (CH3)(2)CHI, n-C4H9I, cyclo-C6H11I, CH3COCl, PhCOCl, (CH3)(3)COCl] in different regioselectivities affording ketones or esters. The square pyramidal bis[n-butyl 2-oxophenyl ketone]nickel(II) complex 16 crystallizes in the monoclinic space group C2/c, while the square planar chloro(phenyl)nickel(II) complex 19 with an ester group in the 2-position crystallizes in the triclinic space group <P(1)over bar>. Steric control of C,C-coupling reactions is demonstrated in three transformations, starting either from (acylphenolato)nickel(II) or from metastable diorganonickel(IV) compounds.

引用

页码：668 / 676

页数：9

共 27 条

[1] MOLECULAR AND CRYSTAL-STRUCTURE OF (TRICYCLOHEXYLPHOSPHINE)METHYLNICKEL(II) 2,4-PENTANEDIONATE - SQUARE-PLANAR COMPLEX CONTAINING A SIGMA-NICKEL-CARBON BOND [J].