A STUDY OF THE ELECTRONIC-STRUCTURES OF BF3 COMPLEXES WITH CARBONYL-COMPOUNDS BY ABINITIO MO METHODS

被引：35

作者：

GUNG, BW

WOLF, MA

机构：

[1] Department of Chemistry, Miami University, Oxford

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1992年 / 57卷 / 05期

关键词：

D O I：

10.1021/jo00031a013

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The syn-CH3CHO.BF3 complex is only 1.22 kcal mol-1 less stable than the corresponding anti-CH3CHO.BF3 complex at the MP2/6-31G* level of theory. The corresponding difference in syn- and anti-PhCHO.BF3 complexes is 5.31 kcal mol-1. The calculated C-C = O (129-degrees) and C-O-B (156-degrees) angles for syn-PhCHO.BF3 complexes have a much greater deviation from the standard geometries of a sp2 orbital than that (123.9-degrees and 125.4-degrees) calculated for syn-CH3CHO.BF3 complexes. A hydrogen-bonding type of attractive interaction between F and H is identified in the syn complexs of acetaldehyde and acetone.

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页码：1370 / 1375

页数：6

相关论文

共 62 条

[1]

ANH NT, 1973, TETRAHEDRON, V29, P3259

[2] LONE PAIR POLAR BOND HYPERCONJUGATION IN CARBON-HALOGEN CHEMISTRY [J].

BINGHAM, RC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1975, 97 (23) :6743-6746

[3] VAN DER WAALS VOLUMES + RADII [J].

BONDI, A .

JOURNAL OF PHYSICAL CHEMISTRY, 1964, 68 (03) :441-+

[4] STEREOSELECTIVE ALDOL REACTIONS WITH ALPHA-UNSUBSTITUTED CHIRAL ENOLATES [J].

BRAUN, M .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1987, 26 (01) :24-37

[5] SNCL4(4-TERT-BUC6H4CHO)2 - X-RAY CRYSTAL-STRUCTURE, SOLUTION NMR, AND IMPLICATIONS FOR REACTIONS AT COMPLEXED CARBONYLS [J].

DENMARK, SE ;

HENKE, BR ;

WEBER, E .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (08) :2512-2514

[6] ON THE LEWIS ACID-INDUCED ADDITION OF ALLYLSTANNANES TO ALDEHYDES - A SPECTROSCOPIC INVESTIGATION [J].

DENMARK, SE ;

WILSON, T ;

WILLSON, TM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (03) :984-986

[7]

DILL JD, 1976, J AM CHEM SOC, V98, P1663, DOI 10.1021/ja00423a004

[8] CRYSTAL AND MOLECULAR-STRUCTURE OF [(CH3)2N]3S+CF3O- - EVIDENCE FOR NEGATIVE FLUORINE HYPERCONJUGATION [J].

FARNHAM, WB ;

SMART, BE ;

MIDDLETON, WJ ;

CALABRESE, JC ;

DIXON, DA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (15) :4565-4567

[9] TILT AND ASYMMETRY OF METHYL-GROUPS IN ASYMMETRIC ENVIRONMENTS [J].

FLOOD, E ;

PULAY, P ;

BOGGS, JE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (17) :5570-5574

[10] INTRINSIC AND EQUILIBRIUM NMR ISOTOPE SHIFT EVIDENCE FOR NEGATIVE HYPERCONJUGATION [J].

FORSYTH, DA ;

YANG, JR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (09) :2157-2161

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