Intra- and intermolecular hydrogen bonding in 2-phosphinylphenol: A quantum chemical study

被引:15
作者
Levy, JB [1 ]
Martin, NH
Hargittai, I
Hargittai, M
机构
[1] Univ N Carolina, Dept Chem, Wilmington, NC 28403 USA
[2] Eotvos Lorand Univ, Hungarian Acad Sci, Struct Chem Res Grp, H-1431 Budapest, Hungary
[3] Tech Univ Budapest, Inst Gen & Analyt Chem, H-1521 Budapest, Hungary
关键词
D O I
10.1021/jp972817t
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
A computational study of 2-phosphinylphenol has been carried out to investigate intramolecular hydrogen bond formation and its consequences in the rest of the molecule. This is an extension of both our synthetic work on organophosphorus derivatives of diphenyl ether and our experimental and computational structure analyses of salicylaldehyde, 2-nitrophenol, and related molecules. Full optimization of the 2-phosphinylphenol geometries was carried out both at the HF/6-31+G** level and, to include electron correlation, at the MP2/ 6-31G* level. The stabilization energy of the intramolecular hydrogen bonding in 2-phosphinylphenol (28.4 kJ/mol by isodesmic calculation) is smaller than that of the intermolecular hydrogen bonding in the dimer of 2-phosphinylphenol, also computed in this work to be 59.1 kJ/mol per hydrogen bond from the counterpoise interaction energy or 57.4 kJ/mol by BSSE-corrected isodesmic calculation. The closure of the six-membered ring with the intramolecular hydrogen bond apparently introduces energy-costing constraints. The geometrical changes in 2-phosphinylphenol accompanying the formation of the hydrogen bond are similar to those observed in 2-nitrophenol and salicylaldehyde, characterized as resonance-assisted hydrogen banding. In addition to the lowest energy monomer with the hydrogen bond, two further stable minima of higher energy with no hydrogen bonding were found for 2-phosphinylphenol.
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页码:274 / 279
页数:6
相关论文
共 17 条
[1]   INTRAMOLECULAR HYDROGEN-BONDING AND MOLECULAR-GEOMETRY OF 2-NITROPHENOL FROM A JOINT GAS-PHASE ELECTRON-DIFFRACTION AND AB-INITIO MOLECULAR-ORBITAL INVESTIGATION [J].
BORISENKO, KB ;
BOCK, CW ;
HARGITTAI, I .
JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (05) :1442-1448
[2]  
Borisenko KB, 1996, J MOL STRUC-THEOCHEM, V388, P107
[3]   Molecular geometry of benzaldehyde and salicylaldehyde: A gas-phase electron diffraction and ab initio molecular orbital investigation [J].
Borisenko, KB ;
Bock, CW ;
Hargittai, I .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (18) :7426-7434
[4]   CALCULATION OF SMALL MOLECULAR INTERACTIONS BY DIFFERENCES OF SEPARATE TOTAL ENERGIES - SOME PROCEDURES WITH REDUCED ERRORS [J].
BOYS, SF ;
BERNARDI, F .
MOLECULAR PHYSICS, 1970, 19 (04) :553-&
[5]  
DHAWAN B, 1990, J CHEM RES-S, P184
[6]  
Frisch M.J., 1995, GAUSSIAN 94
[7]  
GOULD IR, 1994, J MOL STRUCT THEOCHE, V314, P1
[8]   HYDROGEN-BONDS IN SOLUTIONS OF ORTHO PHOSPHORYL SUBSTITUTED PHENOLS [J].
HENNING, HG ;
WILD, W .
JOURNAL FUR PRAKTISCHE CHEMIE, 1976, 318 (01) :69-78
[9]  
LEVY JB, 1997, 1 UNCW MIN S CHEM BI
[10]   CHEMICAL AND PHYSICAL CONSEQUENCES OF 2P-3D OVERLAP IN OMICRON-ANISYLPHOSPHINES AND OMICRON-ANISYLPHOSPHONIUM SALTS [J].
MCEWEN, WE ;
SHIAU, WI ;
YEH, YI ;
SCHULZ, DN ;
PAGILAGAN, RU ;
LEVY, JB ;
SYMMES, C ;
NELSON, GO ;
GRANOTH, I .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1975, 97 (07) :1787-1794