EFFECT OF FLUORINE AND CHLORINE SUBSTITUENTS ON STABILITIES OF DIPHOSPHAALLENE, DIPHOSPHIRENE, AND PHOSPHANYLPHOSPHAALKYNE ISOMERS (XX'CP2 SPECIES WITH X, X' = H, F, AND CL)

被引:19
作者
FITZPATRICK, NJ [1 ]
BROUGHAM, DF [1 ]
GROARKE, PJ [1 ]
NGUYEN, MT [1 ]
机构
[1] UNIV LEUVEN,DEPT CHEM,B-3001 LOUVAIN,BELGIUM
关键词
DIPHOSPHAALLENES; 1H-DIPHOSPHIRENES; 3H-DIPHOSPHIRENES; PHOSPHANYLPHOSPHAALKYNES; CALCULATIONS; AB-INITIO MO;
D O I
10.1002/cber.19941270602
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Ab initio MO calculations at the QCISD(T)/6-31G**//MP2/6-31G** + ZPE level on the XX'CP2 isomers (X = H, F and Cl) show that the energies of the isomeric species are often reordered following halogen substitution. The phosphorus-halogen moiety behaves as the main stabilizing factor on the rest of the molecular structure. This is particularly true when X = F is involved. In the dihalogenated series phosphanylphosphaalkyne (4) becomes the most stable species followed by diphosphaallene (3) and 1H-diphosphirene (6). The effect on the geometry following halogenation is larger if substitution takes place at carbon than at phosphorus. The behaviour of the P species is found to be quite different from, if not opposite to, that of their nitrogen analogues. Finally, the infrared spectra of the most stable isomers are also predicted.
引用
收藏
页码:969 / 978
页数:10
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