STRUCTURE OF OS(CO)4(C2H4), AN OSMACYCLOPROPANE

被引：46

作者：

BENDER, BR ^{[1
]}

NORTON, JR ^{[1
]}

MILLER, MM ^{[1
]}

ANDERSON, OP ^{[1
]}

RAPPE, AK ^{[1
]}

机构：

[1] COLORADO STATE UNIV,DEPT CHEM,FT COLLINS,CO 80523

来源：

ORGANOMETALLICS | 1992年 / 11卷 / 10期

关键词：

D O I：

10.1021/om00046a049

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

1J(C-13-C-13) for an ethylene coordinated to Os(CO)4 has been determined as 39.0 (2) Hz from the H-1 NMR spectrum of Os(CO)4(eta2-(C2H4)-C-13). The molecular structure of Os(CO)4(eta2-C2H4) (1) has been determined by single-crystal X-ray diffraction; 1 crystallizes in space group C2/c with a = 12.271 (5) angstrom, b = 6.778 (1) angstrom, c = 12.345 (4) angstrom, beta = 129.49 (2)-degrees, V = 792.4 (2) angstrom3, and Z = 4. The geometry of 1 is approximately trigonal bipyramidal, with the ethylene carbons twisted out of the equatorial plane by 4.0-degrees. The axial carbonyls of 1 tilt toward the coordinated ethylene, with a C1-Os-C1' angle of 171.3 (5)-degrees. The optimal geometries of Os(CO)4, H2Os(CO)4, and 1 have been calculated by Hartree-Fock methods. The orbital amplitude contour diagrams of a GVB(6/12) wave function for 1 show that the axial bending occurs in order to mix in virtual p, character and improve back-bonding to the equatorial carbonyls; they also show that 1 is best described as a metallacyclopropane.

引用

页码：3427 / 3434

页数：8

共 67 条

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