[(dmpe)_2MnAlH_4]_2和(dmpe)_2MnAlH_4的电子结构和化学键  

THE ELECTRONIC STRUCTURES AND CHEMICAL BONDING IN (dmpe)_2 MnAlH_4 AND [(dmpe)_2 MnAIH_4]_2

作　　者：吴念慈[1] 蔡国强[1] 董南[1] 

机构地区：[1]杭州大学化学系,杭州310028

出　　处：《化学研究与应用》1991年第4期78-81,共4页Chemical Research and Application

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Cp₂BH₄、Cp₂TiBH₄、Cp₂TiAlH₄、（dmpe）₂HCrBH₄、（dmpe）₂HCrAlH₄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.

关 键 词：CNDO/2 铝氢化合物 电子结构 氢桥骨架 

分 类 号：O6[理学—化学]