RELATIONSHIP BETWEEN OLEFINIC PI-COMPLEXES AND 3-MEMBERED RINGS

被引:291
作者
DEWAR, MJS
FORD, GP
机构
[1] Department of Chemistry, University of Texas, Austin, Texas
关键词
D O I
10.1021/ja00498a001
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Compounds with threc-membcred rings can be formulated cither as such or as ir complexes with back-coordination. Dewar first pointed out that olefin transition metal complexes are best represented by the latter structure, a suggestion later confirmed by Chatt and Duncanson in the ease of Zeise&s salt. According to the π-complex theory, compounds of this type can show a continuous range of structures from the π-complex extreme at one end to a “pure” classical ring at the other, so a distinction can be drawn only on the basis of some property that changes along the range. Here we report detailed MNDO calculations for a number of spccies of this type which confirm the postulated continuous transition from w complex to classical ring and which show that the corresponding structural variations can be used to establish a fairly definite order of “π-complex character”. It was originally suggested that the direction of ring opening in unsymmctrically substituted compounds with three-membered rings, brought about by nucleophiles, could be used to distinguish between species best regarded as v complexes and those best regarded as classical microcvcles. A critical survey of the literature suggests that this criterion is generally consistent with the MNDO scale of x-complex character. © 1979, American Chemical Society. All rights reserved.
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页码:783 / 791
页数:9
相关论文
共 90 条
[1]   PERSISTENT COLLISION COMPLEXES IN REACTION OF SILYL IONS WITH ETHYLENE [J].
ALLEN, WN ;
LAMPE, FW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (21) :6816-6822
[2]   STUDY OF VIBRATIONAL FORCE CONSTANTS IN SOME TRANSITION METAL ETHYLENE PI-COMPLEXES [J].
ANDREWS, DC ;
DAVIDSON, G ;
DUCE, DA .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1975, 101 (01) :113-119
[3]   MOLECULAR-ORBITAL THEORY OF ELECTRONIC-STRUCTURE OF MOLECULES .35. BETA-SUBSTITUENT EFFECTS ON STABILITIES OF ETHYL AND VINYL CATIONS - COMPARISON WITH ISOELECTRONIC METHYL BORANES - RELATIVE IMPORTANCE OF HYPERCONJUGATIVE AND INDUCTIVE EFFECT [J].
APELOIG, Y ;
SCHLEYER, PV ;
POPLE, JA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (18) :5901-5909
[4]   MOLECULAR-ORBITAL THEORY OF ELECTRONIC-STRUCTURE OF MOLECULES .33. EFFECT OF ALPHA-ELECTROPOSITIVE SUBSTITUENTS ON STABILITIES OF CARBENIUM IONS [J].
APELOIG, Y ;
SCHLEYER, PV ;
POPLE, JA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (05) :1291-1296
[5]   EXPERIMENTAL EVIDENCE FOR STATISTICAL RANDOMIZATION OF HYDROGEN-ATOMS IN ETHYL CATION [J].
AUSLOOS, P ;
TIERNAN, TO ;
SIECK, LW ;
REBBERT, RE .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (25) :8939-&
[6]  
BEVERLY GM, 1968, CHEM IND-LONDON, P1403
[7]   MECHANISM OF ACID-CATALYSED ALCOHOLYSIS OF EPOXIDES .3. ALCOHOLYSIS OF 1,2-EPOXYPROPANE, 1,2-EPOXY-3-PHENOXYPROPANE, 1,2-EPOXY-3-PHENYLPROPANE, AND 2,3-EPOXYPROPAN-1-OL [J].
BIGGS, J ;
CHAPMAN, NB ;
WRAY, V .
JOURNAL OF THE CHEMICAL SOCIETY B-PHYSICAL ORGANIC, 1971, (01) :66-&
[8]   GROUND-STATES OF MOLECULES .24. MINDO-2 STUDY OF SOME REACTIONS OF CYCLOPROPYLIDENE [J].
BODOR, N ;
DEWAR, MJS ;
MAKSIC, ZB .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (16) :5245-5249
[9]   DETAILED POTENTIAL-ENERGY SURFACES FOR CARBONIUM-ION REARRANGEMENTS - C3H7O+ [J].
BOWEN, RD ;
KALMAN, JR ;
WILLIAMS, DH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (16) :5481-5483
[10]   POTENTIAL SURFACES FOR UNIMOLECULAR REACTIONS OF ORGANIC IONS - C2H6N+ AND C2H5O+ [J].
BOWEN, RD ;
WILLIAMS, DH ;
HVISTENDAHL, G .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (23) :7509-7515