Piesch Martin, Reichl Stephan, Seidl Michael, Balázs Gábor, Scheer Manfred
Institut für Anorganische Chemie, Universität Regensburg, 93040, Regensburg, Germany.
Angew Chem Int Ed Engl. 2021 Jun 25;60(27):15101-15108. doi: 10.1002/anie.202103683. Epub 2021 Jun 1.
A synthetic pathway for the synthesis of novel anionic sandwich complexes with a cyclo-E (E=P, As) ligand as an end deck was developed giving [Cp'''Co(η -E )] (Cp'''=1,2,4-tri-tert-butylcyclopentadienyl, E=P ([5]), As ([6])) in good yields suitable for further reactivity studies. In the reaction with the chlorophosphanes R PCl (R=Ph, Cy, Bu), neutral complexes with a disubstituted cyclo-E P (E=P, As) ligand in [Cp'''Co(η -E PR )] (E=P (7 a-c), As (9 a-c)) were obtained. These compounds can be partially or completely converted into complexes with a cyclo-E (E=P, As) ligand with an exocyclic {PR } unit in [Cp'''Co(η :η -E PR )] (E=P (8 a-c), As (10 a-c)). Additionally, the insertion of the chlorosilylene [LSiCl] (L=( BuN) CPh) into the cyclo-E ligand of [5] and [6] was achieved and the novel heteroatomic complexes [Cp'''Co(η -E SiL)] (E=P (11), As (12)) could be isolated. The reaction pathway was elucidated by DFT calculations.
开发了一种合成新型阴离子夹心配合物的合成途径，该配合物以环-E（E = P，As）配体作为端基，以良好的产率得到[Cp'''Co(η -E )]（Cp''' = 1,2,4-三叔丁基环戊二烯基，E = P ([5])，As ([6])），适合进一步的反应性研究。在与氯膦R PCl（R = Ph，Cy， Bu）的反应中，得到了[Cp'''Co(η -E PR )]（E = P (7 a - c)，As (9 a - c)）中具有二取代环-E P（E = P，As）配体的中性配合物。这些化合物可以部分或完全转化为[Cp'''Co(η :η -E PR )]（E = P (8 a - c)，As (10 a - c)）中具有环外{PR }单元的环-E（E = P，As）配体的配合物。此外，实现了氯硅烯[LSiCl]（L =( BuN) CPh）插入[5]和[6]的环-E配体中，并分离出新型杂原子配合物[Cp'''Co(η -E SiL)]（E = P (11)，As (12)）。通过密度泛函理论计算阐明了反应途径。
