STRUCTURAL EFFECTS ON STABILITIES OF IMINOXY RADICALS

被引:37
作者
BORDWELL, FG
ZHANG, SZ
机构
[1] Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113
关键词
D O I
10.1021/ja00122a016
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The equilibrium acidities for the O-H bonds of seven ketoximes in dimethyl sulfoxide and the oxidation potentials of their conjugate anions have been measured. The combination of the pK(HA) and E(OX)(A(-)) values using eq 1 has allowed estimates to be made of the ethalpies for homolytic cleavage of the O-H bonds (BDEs). The BDEs estimated for the O-H bonds in t-Bu(2)C=NOK-and t-Bu(1-Ad)C=NOH by our simple method using eq 1, BDE = 1.37pK(HA) + 23.1E(OX)(A(-)) + 73.3, were found to be within experimental error of those obtained by a direct calorimetric method. The BDEs of the O-H bonds become progressively weaker as the size of the alkyl groups R and R' in the RR'C=NOH oximes become larger. The BDEs cover a range of 14 kcal/mol from that of 95.8 kcal/mol for the BDE of the O-H bond in Me(2)C=NOH to 81.7 kcal/mol for the BDE of the O-H bond in t-Bu(Ad)C=NOH. The effects are rationalized in terms of increasing ground state energies and decreasing BDEs with increasing size of the alkyl groups, as the result of progressively larger relief of steric strain as the O-H bond is broken homolytically. These and other effects of structural changes in oximes on BDEs of their O-H bonds are consistent with delocalization of the odd electron in a p orbital on oxygen to carbon. The X-ray crystal structure of di-tert-butyl ketoxime has been measured and compared with that of dimethyl ketoxime.
引用
收藏
页码:4858 / 4861
页数:4
相关论文
共 17 条
[1]  
BETHOUX M, 1964, B SOC CHIM FR, P1985
[2]   EFFECTS OF STRUCTURAL-CHANGES ON ACIDITIES AND HOMOLYTIC BOND-DISSOCIATION ENERGIES OF THE N-H BONDS IN PYRIDONES AND RELATED HETEROCYCLES [J].
BORDWELL, FG ;
SINGER, DL ;
SATISH, AV .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (09) :3543-3547
[3]   HOMOLYTIC BOND-DISSOCIATION ENERGIES FOR THE CLEAVAGE OF ALPHA-N-H BONDS IN CARBOXAMIDES, SULFONAMIDES, AND THEIR DERIVATIVES - THE QUESTION OF SYNERGISM IN NITROGEN-CENTERED RADICALS [J].
BORDWELL, FG ;
HARRELSON, JA ;
LYNCH, TY .
JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (10) :3337-3341
[4]   EQUILIBRIUM ACIDITIES AND HOMOLYTIC BOND-DISSOCIATION ENERGIES OF THE H-O BONDS IN OXIMES AND AMIDOXIMES [J].
BORDWELL, FG ;
JI, GZ .
JOURNAL OF ORGANIC CHEMISTRY, 1992, 57 (11) :3019-3025
[5]   EQUILIBRIUM ACIDITIES IN DIMETHYL-SULFOXIDE SOLUTION [J].
BORDWELL, FG .
ACCOUNTS OF CHEMICAL RESEARCH, 1988, 21 (12) :456-463
[6]   SUBSTITUENT EFFECTS ON THE STABILITIES OF PHENOXYL RADICALS AND THE ACIDITIES OF PHENOXYL RADICAL CATIONS [J].
BORDWELL, FG ;
CHENG, JP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (05) :1736-1743
[7]   BOND-DISSOCIATION ENERGIES IN DMSO RELATED TO THE GAS-PHASE [J].
BORDWELL, FG ;
CHENG, JP ;
JI, GZ ;
SATISH, AV ;
ZHANG, XM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (26) :9790-9795
[8]   COUPLING OF ACIDITIES AND OXIDATION POTENTIALS TO ESTIMATE HOMOLYTIC BOND-DISSOCIATION ENERGIES AND RADICAL STABILIZATION ENERGIES [J].
BORDWELL, FG ;
ZHANG, XM ;
FILLER, R .
JOURNAL OF ORGANIC CHEMISTRY, 1993, 58 (22) :6067-6071
[9]   ACIDITIES OF INDENES AND THEIR RADICAL CATIONS - HOMOLYTIC BOND-DISSOCIATION ENERGIES OF THE BENZYLIC C-H BONDS IN INDENES [J].
BORDWELL, FG ;
SATISH, AV .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (26) :10173-10176
[10]   DI TERT BUTYLIMINOXY, A FREE RADICAL OF MODERATE STABILITY [J].
BROKENSHIRE, JL ;
MENDENHALL, GD ;
INGOLD, KU .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1971, 93 (20) :5278-+