SUBSTITUENT EFFECTS IN CLUSTER SPECIES .6. PHOTOELECTRON-SPECTRA OF 5-SUBSTITUTED AND 5,6-SUBSTITUTED 2,4-DICARBA-CLOSO-HEPTABORANE(7)

被引：6

作者：

BELTRAM, GA

JASPERSE, C

CAVANAUGH, MA

FEHLNER, TP

机构：

[1] ST MARYS COLL,DEPT CHEM,NOTRE DAME,IN 46556

[2] UNIV NOTRE DAME,DEPT CHEM,NOTRE DAME,IN 46556

来源：

INORGANIC CHEMISTRY | 1990年 / 29卷 / 02期

关键词：

D O I：

10.1021/ic00327a035

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The He and I photoelectron spectra of 2-X-2,4-C2B5H6and 5,6-X2-2,4-C2B5H5, where X = Cl, Br, and I, are reported. After inductive effects are taken into account, π-type interactions between cluster surface (π-endo) orbitals and filled halogen p orbitals successfully account for the effects of halogen substitution on the photoelectron spectra of the substituted carborane. The results permit comparison of the nature of the 5- and 6-positions relative to sites for substitution in other borane and carborane cages and also of the extent of interaction of X with a seven-membered cluster relative to that with clusters having three to ten members. This work reinforces the idea that the surface orbitals of a cluster play an important role in determining the effect of substitution on cluster properties. © 1990, American Chemical Society. All rights reserved.

引用

页码：329 / 335

页数：7

共 27 条

[1] SUBSTITUENT EFFECTS ON CLOSO-2,4-C2B5H7 DERIVATIVE REARRANGEMENT RATES - COMPARISON OF REARRANGEMENT PATTERN AND RATE CONSTANTS OF A MIXED DISUBSTITUTED CARBORANE, 5-CH3-6-CL-2,4-C2B5H5, WITH THOSE OF MONOSUBSTITUTED 5-CH3-2,4-C2B5H6, 5-CL-2,4-C2B5H6 AND DISUBSTITUTED 5,6-(CH3)2-2,4-C2B5H5, 5,6-CL2-2,4-C2B5H5 - MECHANISTIC IMPLICATIONS AND ISOMER STABILITY CORRELATIONS [J].