摘要
70年代中期,已有不少作者对过渡元素硼氢化合物进行研究。但对过渡元素铝氢化合物的研究是近几年才开始的。这两类化合物的化学行为有着显著差异,通常,硼以四配位单个形式存在,而铝则以五配位双聚形式存在,我们曾用CNDO/2研究了Cp<sub>2</sub>BH<sub>4</sub>、Cp<sub>2</sub>TiBH<sub>4</sub>、Cp<sub>2</sub>TiAlH<sub>4</sub>、（dmpe）<sub>2</sub>HCrBH<sub>4</sub>、（dmpe）<sub>2</sub>HCrAlH<sub>4</sub>以及其它一些Ti的五配位铝化合物的电子结构,较合理地解释了这一现象。
A theoretical study on the electronic structures or (dmpe)_2 MnAlH_4 (Ⅰ) and [(dmpe)_2MnAlH_4]_2 (Ⅱ) (here, dmpe=(CH_3)_2PCH_2CH_2P(CH_3)_2, we have used two PH_3 instead of dmpe in calculations) has been carried out by CNDO/2 method. The results showed: (1) The bridge hydrogen skeleton Mn(u-H)_2 Al in (Ⅰ) has comparatively large contribution to higher occupied MO_3 but in (Ⅱ), Al-H_2 (H_2 is terminal hydrogen atom) has comparatively large contribution to higher occupied MO. (2) Al(u0H)_2 Al in (Ⅱ) has lower energy. These may be the reasons that the molecule exists in (Ⅱ) not in (Ⅰ) in solid state.
出处
《化学研究与应用》
CAS
CSCD
1991年第4期78-81,共4页
Chemical Research and Application
关键词
CNDO/2
铝氢化合物
电子结构
氢桥骨架
CNDO/2
hydroaluminium
electronic structures
bridge hydrogen skelwton
