SYNTHESIS, CRYSTAL-STRUCTURE AND SPECTROSCOPIC PROPERTIES OF THE CLUSTER ANIONS [(MO6BR8I)X(6)(A)](2-) WITH X(A)=F, CL, BR, I

被引：62

作者：

PREETZ, W

BUBLITZ, D

VONSCHNERING, HG

SASSMANNSHAUSEN, J

机构：

[1] CHRISTIAN ALBRECHTS UNIV KIEL,INST ANORGAN CHEM,W-2300 KIEL 1,GERMANY

[2] MAX PLANCK INST FESTKORPERFORSCH,W-7000 STUTTGART 1,GERMANY

来源：

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE | 1994年 / 620卷 / 02期

关键词：

OCTA-MU-BROMO-HEXAHALOGENO-OCTAHEDRO-HEXAMOLYBDATE(2-)-ANIONS; SYNTHESIS; CRYSTAL STRUCTURE; RAMAN; IR SPECTRA; NORMAL COORDINATE ANALYSIS; MO-95; NMR; F-19;

D O I：

10.1002/zaac.19946200207

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The tetrabutylammonium (TBA), tetraphenylphosphonium (TPP) and tetraphenylarsonium (TPAs) salts of the octa-mu3-bromo-hexahalogeno-octahedro-hexamolybdate(2 -) anions [(Mo6Br8i)X6a]2- (X(a) - F, Cl, Br, 1) are synthesized from solutions of the free acids H2[(MO6Br8i)X6a] . 8 H2O with X(a) Cl, Br, I. The crystal structures show systematic stretchings in the Mo-Mo bond length and a slight compression of the Br8i cube in the F(a) to I(a) series. The cations do not change much. The i. r. and Raman spectra show at 10 K almost constant frequencies of the (Mo6Br8i) cluster vibrations, whereas all modes with X(a) ligand contribution are characteristically shifted. The most important bands are assigned by polarization measurements and the force constants are derived from normal coordinate analysis. The Mo-95 nmr signals are shifted to lower field with increasing electronegativity of the X(a) ligands. The fluorine compound shows a sharp F-19 nmr singlet at -184.5 ppm.

引用

页码：234 / 246

页数：13

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