Barthélemy Antoine, Scherer Harald, Daub Michael, Bugnet Alexis, Krossing Ingo
Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Universität Freiburg, Albertstr. 21, 79104, Freiburg, Germany.
Angew Chem Int Ed Engl. 2023 Nov 20;62(47):e202311648. doi: 10.1002/anie.202311648. Epub 2023 Oct 17.
The reaction of bisdicyclohexylphosphinoethane (dcpe) and the subvalent M sources [M (PhF) ][pf] (M=Ga , In ; [pf] =[Al(OR ) ] ; R =C(CF ) ) yielded the salts [{M(dcpe)} ][pf] , containing the first dicationic, trans-bent digallene and diindene structures reported so far. The non-classical M ⇆M double bonds are surprisingly short and display a ditetrylene-like structure. The bonding situation was extensively analyzed by quantum chemical calculations, QTAIM (Quantum Theory of Atoms in Molecules) and EDA-NOCV (Energy Decomposition Analysis with the combination of Natural Orbitals for Chemical Valence) analyses and is compared to that in the isoelectronic and isostructural, but neutral digermenes and distannenes. The dissolved [{Ga(dcpe)} ] ([pf] ) readily reacts with 1-hexene, cyclooctyne, diphenyldisulfide, diphenylphosphine and under mild conditions at room temperature. This reactivity is analyzed and rationalized.
双环己基膦基乙烷（dcpe）与低价态M源[M(PhF)][pf]（M = Ga，In；[pf] = [Al(OR) ]；R = C(CF) ）反应生成盐[{M(dcpe)} ][pf]，其中包含迄今为止报道的首个双阳离子、反式弯曲的双镓烯和双铟烯结构。非经典的M⇆M双键出奇地短，并呈现出类似双四元烯的结构。通过量子化学计算、QTAIM（分子中原子的量子理论）和EDA-NOCV（结合化学价自然轨道的能量分解分析）分析对键合情况进行了广泛研究，并与等电子、等结构但为中性的二锗烯和二锡烯中的键合情况进行了比较。溶解的{Ga(dcpe)} 在室温下的温和条件下能与1-己烯、环辛炔、二苯基二硫醚、二苯基膦迅速反应。对这种反应活性进行了分析并给出了合理的解释。
