Abstract
A synthetic pathway for the synthesis of novel anionic sandwich complexes with a cyclo-E3 (E=P, As) ligand as an end deck was developed giving [Cp′′′Co(η3-E3)]− (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 R2PCl (R=Ph, Cy, tBu), neutral complexes with a disubstituted cyclo-E3P ...
Abstract
A synthetic pathway for the synthesis of novel anionic sandwich complexes with a cyclo-E3 (E=P, As) ligand as an end deck was developed giving [Cp′′′Co(η3-E3)]− (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 R2PCl (R=Ph, Cy, tBu), neutral complexes with a disubstituted cyclo-E3P (E=P, As) ligand in [Cp′′′Co(η3-E3PR2)] (E=P (7 a–c), As (9 a–c)) were obtained. These compounds can be partially or completely converted into complexes with a cyclo-E3 (E=P, As) ligand with an exocyclic {PR2} unit in [Cp′′′Co(η2:η1-E3PR2)] (E=P (8 a–c), As (10 a–c)). Additionally, the insertion of the chlorosilylene [LSiCl] (L=(tBuN)2CPh) into the cyclo-E3 ligand of [5] and [6] was achieved and the novel heteroatomic complexes [Cp′′′Co(η3-E3SiL)] (E=P (11), As (12)) could be isolated. The reaction pathway was elucidated by DFT calculations.
Ein synthetischer Zugang zur Synthese neuartiger anionischer Sandwichkomplexe mit einem cyclo-E3-Liganden (E=P, As) als Enddeck wurde entwickelt, der [Cp′′′Co(η3-E3)]− (Cp′′′=1,2,4-Tri-tert-butylcyclopentadienyl; E=P ([5]), As ([6])) in guten Ausbeuten ergibt und damit diese für weitere Reaktivitätsstudien geeignet macht. In der Reaktion mit den Chlorophosphanen R2PCl (R=Ph, Cy, tBu) wurden neutrale Komplexe mit einem zweifach substituierten cyclo-E3P-Liganden (E=P, As) in [Cp′′′Co(η3-E3PR2)] (E=P (7 a–c), As (9 a–c)) erhalten. Diese Verbindungen können teilweise oder vollständig in Komplexe mit einem cyclo-E3-Liganden mit einer exocyclischen {PR2}-Einheit in [Cp′′′Co(η2:η1-E3PR2)] (E=P (8 a–c), As (10 a–c)) transferiert werden. Darüber hinaus gelang es, das Chlorosilylen [LSiCl] (L=(tBuN)2CPh) in den cyclo-E3-Liganden von [5] und [6] zu insertieren und die neuartigen heteroatomaren Komplexe [Cp′′′Co(η3-E3SiL)] (E=P (11), As (12)) zu isolieren. Der Reaktionsweg konnte durch DFT-Rechnungen aufgeklärt werden.
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