THEORETICAL-STUDY OF THE REACTIONS OF ETHENE WITH DIIMIDE SPECIES

被引:62
作者
PASTO, DJ
CHIPMAN, DM
机构
[1] UNIV LOUIS PASTEUR STRASBOURG,INST CHEM,STRASBOURG,FRANCE
[2] UNIV NOTRE DAME,RADIAT LAB,NOTRE DAME,IN 46556
关键词
D O I
10.1021/ja00503a007
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Ab initio SCF calculations have been carried out on the minimum energy pathways for reduction of ethane by cis-, trans-, and 1, 1-diimide. cis-and 1, 1-diimide each undergo synchronous transfer of hydrogen to ethene (diimide reduction) with 4-31G energy barriers of 26.7 and 45.8 kcal/mol, respectively. The present result with m-diimide is in distinct contrast with the results of a previous calculation which gave an energy barrier of ~60 kcal/mol. trans-Diimide reacts with ethene by either of two equally favorable pathways: (1) an indirect process corresponding to piior isomerization to m-diimide with a 4-31G energy barrier of 46.0 kcal/mol; (2) a direct 1, 3-addition to ethene to produce ethylaminonitrene with a 4-31G energy barrier of 45.3 kcal/mol. Various modes of decomposition of alkylamino-and dialkylaminonitrenes have been explored, the most favorable pathway apparently being a two-step, homolytic dissociation in which cleavage of the first C-N bond is the slow step. Concerted rearrangement of aminonitrene to trns-diimide is a “forbidden” process possessing a 4-31G energy barrier of 81.5 kcal/mol. The results of this theoretical study are discussed in terms of the known experimental facts on the diimide reduction reaction and decomposition of dialkylaminonitrenes. © 1979, American Chemical Society. All rights reserved.
引用
收藏
页码:2290 / 2296
页数:7
相关论文
共 41 条
[1]   AB-INITIO STUDY OF ELECTRONIC-STRUCTURE OF DIIMIDE [J].
AHLRICHS, R ;
STAEMMLER, V .
CHEMICAL PHYSICS LETTERS, 1976, 37 (01) :77-81
[2]  
BAIRD NC, 1977, CAN J CHEM, V55, P350, DOI 10.1139/v77-052
[3]   QUANTUM ORGANIC PHOTOCHEMISTRY .4. PHOTOISOMERIZATION OF DIIMIDE AND AZOALKANES [J].
BAIRD, NC ;
SWENSON, JR .
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1973, 51 (18) :3097-3101
[4]   SINGLET AND TRIPLET-STATES OF AMINONITRENES - AB-INITIO MOLECULAR-ORBITAL STUDY [J].
BAIRD, NC ;
BARR, RF .
CANADIAN JOURNAL OF CHEMISTRY, 1973, 51 (20) :3303-3308
[5]   INFRARED SPECTRUM + STRUCTURE OF DIIMIDE [J].
BLAU, EJ ;
HOCHHEIMER, BF .
JOURNAL OF CHEMICAL PHYSICS, 1964, 41 (05) :1174-&
[6]   INFRARED SPECTRUM OF DIIMIDE [J].
BLAU, EJ ;
HOCHHEIMER, BF ;
UNGER, HJ .
JOURNAL OF CHEMICAL PHYSICS, 1961, 34 (03) :1060-&
[7]   THEORETICAL DESCRIPTION OF TRANS-CIS CONVERSION IN LOWEST EXCITED-STATES OF DIIMIDE - COMPARISON OF DIFFERENT METHODS FOR CALCULATION OF EXCITED-STATE WAVE-FUNCTIONS [J].
CIMIRAGLIA, R ;
RIERA, JM ;
TOMASI, J .
THEORETICA CHIMICA ACTA, 1977, 46 (03) :223-235
[8]   CHEMISTRY OF DIMIDE .3. HYDROGEN TRANSFER TO MULTIPLE BONDS BY DISSOCIATION OF DIIMIDE-ANTHRACENE ADDUCT, ANTHRACENE-9,10-BIMINE [J].
COREY, EJ ;
MOCK, WL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1962, 84 (04) :685-&
[9]  
COREY EJ, 1961, TETRAHEDRON LETT, P347
[10]  
COREY EJ, 1961, J AM CHEM SOC, V83, P2956