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
相关论文
共 20 条
  • [11] MOLECULAR-STRUCTURE AND SPECTROSCOPIC PROPERTIES OF CARBODIIMIDE (HN=C=NH)
    NGUYEN, MT
    RIGGS, NV
    RADOM, L
    WINNEWISSER, M
    WINNEWISSER, BP
    BIRK, M
    [J]. CHEMICAL PHYSICS, 1988, 122 (02) : 305 - 315
  • [12] SYNTHESIS AND STRUCTURE OF A 1H-DIPHOSPHIRENE
    NIECKE, E
    STREUBEL, R
    NIEGER, M
    STALKE, D
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1989, 28 (12): : 1673 - 1674
  • [13] FORMATION OF A TRANS-1,2,4,5-TETRAPHOSPHATRICYCLO-[3.1.0.0/2,4]HEXANE BY [2+2]-CYCLODIMERIZATION OF A 3H-DIPHOSPHIRENE
    NIECKE, E
    STREUBEL, R
    NIEGER, M
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1991, 30 (01): : 90 - 91
  • [14] Niecke E., 1991, ANGEW CHEM, V103, P103
  • [15] Niecke E., 1989, ANGEW CHEM, V101, P1708
  • [16] 3.3-DIALKYL-DIAZACYCLOPROPEN-(1)
    PAULSEN, SR
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1960, 72 (21) : 781 - 782
  • [17] THE ANOMERIC EFFECT WITH CENTRAL ATOMS OTHER THAN CARBON .1. STRONG-INTERACTIONS BETWEEN NONBONDED SUBSTITUENTS IN POLYFLUORINATED 1ST-ROW AND 2ND-ROW HYDRIDES
    REED, AE
    SCHLEYER, PV
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (24) : 7362 - 7373
  • [18] SCHOELLER WW, 1993, J MOL STRUC-THEOCHEM, V284, P61
  • [19] ISOLATION AND CHARACTERIZATION OF THE 1ST STABLE DIPHOSPHA-ALLENE - P,P'-BIS(2,4,6-TRI-T-BUTYLPHENYL)-1,3-DIPHOSPHA-ALLENE
    YOSHIFUJI, M
    TOYOTA, K
    INAMOTO, N
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1984, (11) : 689 - 690
  • [20] [No title captured]