BONDING IN YXXY DIHALIDES AND DIHYDRIDES OF DIOXYGEN AND DISULFUR

被引:26
作者
ALLERES, DR
COOPER, DL
CUNNINGHAM, TP
GERRATT, J
KARADAKOV, PB
RAIMONDI, M
机构
[1] UNIV LIVERPOOL,DEPT CHEM,LIVERPOOL L69 3BX,MERSEYSIDE,ENGLAND
[2] UNIV BRISTOL,SCH CHEM,BRISTOL BS8 1TS,AVON,ENGLAND
[3] UNIV MILAN,DIPARTIMENTO CHIM FIS & ELETTROCHIM,I-20133 MILAN,ITALY
来源
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS | 1995年 / 91卷 / 19期
关键词
D O I
10.1039/ft9959103357
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Ab initio calculations based on spin-coupled theory are used to compare and contrast the bonding in FOOF, HOOH, FSSF, CISSCI and HSSH, with emphasis on rationalising the striking variations in bond length. The resulting modern VB descriptions of the X-Y sigma-like bonds closely parallel those for the analogous XY(2) species, except for the expected changes to the orbital overlaps induced by the different bond lengths. In examining the variations in geometry, it seems that the most relevant aspect of, the bonding is that provided by the various p(pi)-like orbitals. In FOOF, FSSF and, to a lesser extent, CISSCI, incipient hypercoordinate character is observed (at oxygen or sulfur), with two partial pi-like interactions in approximately perpendicular planes, as well as some antibonding character in the X-Y bonds.
引用
收藏
页码:3357 / 3362
页数:6
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