Using the Al precursor Cp Al in conjunction with triphosphiranes (PAr) (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 [Cp Al(μ-PMes)] 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)] (Ar=Dip, Tip) and additionally add the phosphorus variants [Cp*Al(μ-PAr)] (P=Mes, Dip, Tip). The reactivity of one variant [Cp Al(μ-PPh)] towards NHCs was tested and resulted in double NHC-stabilised [Cp (IiPr )Al(μ-PPh)] .
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| http://dx.doi.org/10.1002/anie.202111121 | DOI Listing |
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