The gas-phase conformation of 3,7-dimethyl-3,7-diazabicyclo[3.3.1]nonane |
| |
Authors: | P Livant KA Roberts MD Eggers SD Worley |
| |
Institution: | Department of Chemistry, Auburn University, AL 36849, U.S.A. |
| |
Abstract: | The gas-phase conformation of the title compound (1) is discussed in reference to its photoelectron spectrum. The experimental lone-pair/lone-pair splitting (0.51 eV), when compared with that of similar diamines and with the results of three sets of MO calculations (MINDO/3, MNDO and STO-3G), leads to the conclusion that 1 exists in the chair-chair conformation. A remarkable sensitivity of the calculations to slight changes in the geometry is noted, and it is suggested that calculations of this type must include geometry-optimization. The question of through-space vs through-bond inteaction of the nitrogen lone pairs was explored by performing MNDO calculations in which the N-N resonance integrals were set to zero. These calculations indicate that in the chair-chair conformation the N-N interaction is mainly through-space. The 13CNMR and Ni(acac)2-induced 13C shifts of 1 are discussed. |
| |
Keywords: | |
本文献已被 ScienceDirect 等数据库收录! |
|