Cyclo‐Dipnictadialanes (original) (raw)

Angewandte Chemie International Edition, 2021

Abstract

Abstract Using the AlI precursor Cp3tAl in conjunction with triphosphiranes (PAr)3 (Ar=Mes, Dip, Tip) we have succeeded in preparing Lewis base‐free cyclic diphosphadialanes with both the Al and P atoms bearing three substituents. Using the sterically more demanding Dip and Tip substituents the first 1,2‐diphospha‐3,4‐dialuminacyclobutanes were obtained, whereas with Mes substituents [Cp3tAl(μ‐PMes)]2 is formed. This divergent reactivity was corroborated by DFT studies, which indicated the thermodynamic preference for the 1,2‐diphospha‐3,4‐dialuminacyclobutane form for sterically more demanding groups on phosphorus. Using Cp*Al we could extend this concept to the corresponding cyclic diarsadialanes [Cp*Al(μ‐AsAr)]2 (Ar=Dip, Tip) and additionally add the phosphorus variants [Cp*Al(μ‐PAr)]2 (P=Mes, Dip, Tip). The reactivity of one variant [Cp3tAl(μ‐PPh)]2 towards NHCs was tested and resulted in double NHC‐stabilised [Cp3t(IiPr2)Al(μ‐PPh)]2.

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