SYNTHESIS AND STRUCTURE OF THE NIOBIUM(III) PHOSPHIDO COMPLEX (C5H5)2NB(CO)(PIPRPH) - EFFICIENT GAUCHE EFFECT AND LOW INVERSION BARRIER IN BENT-METALLOCENE CHEMISTRY

被引：48

作者：

BONNET, G

KUBICKI, MM

MOISE, C

LAZZARONI, R

SALVADORI, P

VITULLI, G

机构：

[1] UNIV BOURGOGNE,FAC SCI,CNRS,SYNTH & ELECTROSYNTH ORGANOMET LAB,URA 33,6 BLVD GABRIEL,F-21000 DIJON,FRANCE

[2] UNIV PISA,DIPARTIMENTO CHIM & CHIM IND,I-56100 PISA,ITALY

[3] CNR,CTR STUDIO MACROMOLEC STEREORDINATE & OTTICAMENTE ATT,I-56100 PISA,ITALY

来源：

ORGANOMETALLICS | 1992年 / 11卷 / 02期

关键词：

D O I：

10.1021/om00038a071

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction of Cp2Nb(CO)H with P(i)PrPhCl afforded the ionic product [Cp2Nb(CO)(P(i)PrPhH)]Cl, which upon treatment with NaOH gives the neutral niobium phosphido complex Cp2Nb(CO)(P(i)PrPh) (1). 1 crystallizes in the monoclinic space group P2(1)/c, with a = 16.899 (3) angstrom, b = 15.409 (2) angstrom, c = 13.717 (3) angstrom, beta = 90.94 (2)-degrees, V = 3571.2 angstrom 3, Z = 8, and R = 0.038, with two independent chiral molecules in the asymmetric unit of the unit cell. One of them is related to the other by rough translation by a half of the lattice vector a. The torsion angles in both molecules involving the metal and the phosphorus lone pairs are close to 73-degrees, thus indicating an efficient operation of the ''gauche effect''. The origin of the observed low inversion barrier at phosphorus is discussed.

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页码：964 / 967

页数：4

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