biostudies-literatureNees SDeutsche ForschungsgemeinschaftKlaus Tschira StiftungAlexander von Humboldt-StiftungCoordenação de Aperfeiçoamento de Pessoal de Nível SuperiorBoehringer Ingelheim Stiftung24318-24325https://www.ebi.ac.uk/biostudies/studies/S-EPMC8596407biostudies-literatureUnknown60(45)Using the Al^I precursor Cp^3t Al 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 [Cp^3t Al(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) anAngewandte Chemie (International ed. in English)Cyclo-Dipnictadialanes.PMC8596407Exploration GrantKlaus Tschira Boost FundNees SGoettel JTBraunschweig HFantuzzi FHering-Junghans CFischer MHarterich MWellnitz THofmann ASiewert JEfalseCyclo-Dipnictadialanes.Using the Al^I precursor Cp^3t Al 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 [Cp^3t Al(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) an2021-01-01T00:00:00Z2021 Nov2026-07-16T16:57:18.325Z2022-02-11T13:05:35.058ZS-EPMC85964073447823110.1002/anie.202111121