SYNTHESIS, STRUCTURE, AND ELECTRONIC-PROPERTIES OF BIS(TETRAMETHYLCYCLOPROPYLIDENE)METHANE AND BIS(CYCLOPROPYLIDENE)METHANE

被引:13
作者
ECKERTMAKSIC, M
ZOLLNER, S
GOTHLING, W
BOESE, R
MAKSIMOVIC, L
MACHINEK, R
DEMEIJERE, A
机构
[1] UNIV HAMBURG, INST ORGAN CHEM, W-2000 HAMBURG 13, GERMANY
[2] UNIV GESAMTHSCH ESSEN, INST ANORGAN CHEM, W-4300 ESSEN, GERMANY
[3] UNIV GOTTINGEN, INST ORGAN CHEM, W-3400 GOTTINGEN, GERMANY
来源
CHEMISCHE BERICHTE-RECUEIL | 1991年 / 124卷 / 07期
关键词
ALLENES; HIGHLY STRAINED; STRAIN STRUCTURE CORRELATION; HYBRIDIZATION EFFECTS; C-13; C-13 COUPLING CONSTANTS; CALCULATIONS;
D O I
10.1002/cber.19911240720
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Bis(tetramethylcyclopropylidene)methane (5) was prepared by treating 1-(dichloroethenylidene)-2,2,3,3-tetramethylcyclopropane (3) with tert-butyllithium in the presence of 2,3-dimethyl-2-butene. The parent allene 6 was obtained along a new route from bis(1-bromocyclopropyl) ketone (11) with low-valent titanium. Both 5 and 6 show unusually intense allene stretching bands in the IR spectra, and the signals of their central carbon atoms appear at remarkably high field in the C-13-NMR spectra. The unique structural features of 5 and 6, as evidenced by an X-ray crystal structural analysis of 5 and 1J(cc) values, agree remarkably well with theoretical predictions made by semiempirical (MNDO) and ab initio (4-31G) calculations and on the basis of the simple picture offered by the hybridization model using the iterative maximum overlap (IMO) approach.
引用
收藏
页码:1591 / 1596
页数:6
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