ON HETEROCYCLIC-SYSTEMS CONTAINING BISMUTH(III) .2. 8-MEMBERED HETEROCYCLES CL/BR/I-M(CH2CH2CH2)(2)X WITH LEWIS ACIDIC GROUP 15 ATOMS M =AS, SB, BI AND DONOR ATOMS X=NR, S - A CONTRIBUTION TO THE VALUE OF THE ELECTRONEGATIVITY OF BISMUTH(III)

被引：10

作者：

BRAU, E ^{[1
]}

FALKE, R ^{[1
]}

ELLNER, A ^{[1
]}

BEUTER, M ^{[1
]}

KOLB, U ^{[1
]}

DRAGER, M ^{[1
]}

机构：

[1] JOHANNES GUTENBERG UNIV,INST ANORGAN CHEM & ANALYT CHEM,D-55099 MAINZ,GERMANY

来源：

POLYHEDRON | 1994年 / 13卷 / 03期

关键词：

D O I：

10.1016/S0277-5387(00)81647-2

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Paths to the ligands (Cl/Br-CH2CH2CH2)(2)NR/O/S/Se, R = Me, Bz, iPr, iBu, to the diGrignard reagents (Cl/BrMg-CH2CH2CH2)(2)NR/O/S, R = Me, Bz, iPr, iBu and to the eight-membered group 15 heterocycles (C1/Br/I-As/Sb/Bi(CH2CH2CH2)(2)NR/S, R = Me, Bz, iBu are given. C-13-NMR, TR and Raman spectra are discussed; for the compound ClSb(CH2CH2CH2)(2)NMe the crystal structure analysis is given: the antimony atom is clearly Lewis acidic with psi-trigonal-bipyramidal coordination and a transannular Sb ... N interaction of 2.385(2) Angstrom. For such a configuration the values of the C-13-NMR chemical shifts of the alpha-CH2-groups (e.g. Cl-As/Sb/Bi(alpha CH2CH2CH2)(2)NMe 34.6, 25.9, 46.6 ppm) display clearly a sequence N > Bi > P approximate to As > Sb for the Paulins electronegativities of the group 15 elements: a value as high as 2.3 for bismuth is suggested.

引用

页码：365 / 374

页数：10

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