Department of Chemistry, P.O. Box 35, FI-40014 University of Jyväskylä, Finland.
Inorg Chem. 2010 Dec 6;49(23):10992-1000. doi: 10.1021/ic101487g. Epub 2010 Nov 4.
The nature of metal-metal bonding in group 13 dimetallenes REER (E = Al, Ga, In, Tl; R = H, Me, (t)Bu, Ph) was investigated by use of quantum chemical methods that include HF, second order Møller-Plesset perturbation theory (MP2), coupled cluster (CCSD(T)), complete active space with (CASPT2) and without (CAS) second order perturbation theory, and two density functionals, namely, B3LYP and M06-2X. The results show that the metal-metal interaction in group 13 dimetallenes stems almost exclusively from static and dynamic electron correlation effects: both dialuminenes and digallenes have an important singlet diradical component in their wave function, whereas the bonding in the heavier diindenes and, in particular, dithallenes is dominated by closed shell metallophilic interactions. The reported calculations represent a systematic attempt to determine the metal and ligand dependent bonding changes in these systems.
通过使用包括 HF、二级 Møller-Plesset 微扰理论 (MP2)、耦合簇 (CCSD(T))、完整活性空间 (CASPT2) 和不包括二级微扰理论 (CAS) 以及两种密度泛函（B3LYP 和 M06-2X）在内的量子化学方法，研究了第 13 族二金属烯 REER（E=Al、Ga、In、Tl；R=H、Me、(t)Bu、Ph）中金属-金属键的性质。结果表明，第 13 族二金属烯中的金属-金属相互作用几乎完全源于静态和动态电子相关效应：双铝烯和双镓烯在其波函数中都具有重要的单重自由基分量，而较重的二茚烯和特别是双铊烯中的键合则由封闭壳层的金属亲合相互作用主导。所报道的计算代表了系统地确定这些体系中金属和配体依赖性键合变化的尝试。
