SPECTROSCOPIC AND THEORETICAL-ANALYSIS OF THE INTENSE T-1(1U) ]-A-1(1G) TRANSITIONS IN MO(CO)6 AND W(CO)6

被引：37

作者：

TROGLER, WC ^{[1
]}

DESJARDINS, SR ^{[1
]}

SOLOMON, EI ^{[1
]}

机构：

[1] MIT,DEPT CHEM,CAMBRIDGE,MA 02139

来源：

INORGANIC CHEMISTRY | 1979年 / 18卷 / 08期

关键词：

D O I：

10.1021/ic50198a016

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Optical spectra of M(CO)6 (M = Mo, W) complexes have been measured in argon matrices at 10 K, focusing on the intense 1Tlu 1Alg transitions at 286 and 230 nm. Vibrational structure is observed on the 286-nm band. A detailed band shape analysis is performed on both absorption bands, and accurate excited-state electronic parameters are obtained. The distortion of the CO moiety is found to be small for both transitions, particularly for the 286-nm one. Transition-state X± calculations have been performed for the low-lying allowed metal to ligand and ligand to metal charge-transfer transitions as well as for the metal-localized d(t2g) p(tlu) excitation. The results confirm assignment of the electronic absorption bands to d(t2g) CO(Π)(tlu and t2u); however, the IT* levels of CO in the metal hexacarbonyls prove to differ considerably from the IT* level in free CO. Relative amounts of charge reorganization calculated for the excited states provide a rationale of the spectroscopically derived parameters. © 1979, American Chemical Society. All rights reserved.

引用

页码：2131 / 2136

页数：6

共 29 条

[1] EFFICIENT NUMERICAL MULTICENTER BASIS SET FOR MOLECULAR-ORBITAL CALCULATIONS - APPLICATION TO FECL4 [J].