THE PREPARATION AND CHARACTERIZATION OF M2(OEPH3)2(NME2)4, WHERE M = MO AND W AND E = C AND SI - THE X-RAY CRYSTAL-STRUCTURES OF GAUCHE-W2(OCPH3)2(NME2)4, ANTI-MO2(OCPH3)2(NME2)4 AND ANTI-W2(OSIPH3)2(NME2)4

被引：12

作者：

CHISHOLM, MH ^{[1
]}

PARKIN, IP ^{[1
]}

HUFFMAN, JC ^{[1
]}

LOBKOVSKY, EM ^{[1
]}

FOLTING, K ^{[1
]}

机构：

[1] INDIANA UNIV,CTR MOLEC STRUCT,BLOOMINGTON,IN 47405

来源：

POLYHEDRON | 1991年 / 10卷 / 23-24期

基金：

欧洲研究理事会;

关键词：

D O I：

10.1016/S0277-5387(00)86188-4

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction of M2(NMe2)6 (M = Mo, W) with triphenylmethanol in hexane/ether produces M2(OCPh3)2(NMe2)4 (I) as yellow crystals in high yield (92-97%). M2 (OCPh3)2(NMe2)4 are air-sensitive, soluble in aromatic solvents and decompose around 160-degrees-C. The H-1 NMR of I is temperature dependent and shows a mixture of anti and gauche rotamers. The X-ray crystal structures of I reveal exclusively the gauche isomer for tungsten and the anti isomer for molybdenum. The reactions between M2(NMe2)6 and triphenylsilanol (2 equiv.) yield M2(OSiPh3)2(NMe2)4 compounds (M = Mo, W) (II) as orange crystals. In the presence of > 6 equiv. of Ph3SiOH the M2(NMe2)6 compounds react further to give yellow crystalline compounds, M2(OSiPh3)4(NMe2)2. In compound II, where M = W, the W2O2N4 skeleton adopted the anti conformation with W-W = 2.2954(6) angstrom, W-O = 1.925(4) angstrom, W-N = 1.935(8) angstrom, W-W-O = 108.1(1)-degrees, W-W-N = 102(1)-degrees. The addition of Ph3SiOH (> 6 equiv.) to W2(OBu(t))6 yielded the related compound W2 (OBu(t))2(OSiPh3)4.

引用

页码：2839 / 2846

页数：8

共 15 条

[1]

ABBOTT RG, 1990, INORG CHEM, V9, P1829

[2] TUNGSTEN-TUNGSTEN TRIPLE BOND .8. DINUCLEAR ALKOXIDES OF TUNGSTEN(III) AND STRUCTURAL CHARACTERIZATION OF HEXAISOPROPOXYBIS(PYRIDINE)DITUNGSTEN, THE 1ST COMPOUND WITH 4-COORDINATED TUNGSTEN ATOMS UNITED BY A TRIPLE BOND [J].