Aluminium Diphosphamethanides: Hidden Frustrated Lewis Pairs. Issue 28 (8th June 2016)

• Record Type: Journal Article
• Authors: Styra, Steffen; Radius, Michael; Moos, Eric; Bihlmeier, Angela; Breher, Frank
• Is Part Of: Chemistry. Volume 22:Issue 28(2016)
• Page Start: 9508
• Page End: 9512
• Publication Date: 2016-06-08
• Subjects: aluminium -- frustrated Lewis pairs -- hydrogen -- phosphorus; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201602192
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The synthesis and characterisation of two aluminium diphosphamethanide complexes, [Al( t Bu)2 {κ 2 P, P′ ‐Mes*PCHPMes*}] (3 ) and [Al(C6 F5 )2 {κ 2 P, P′ ‐Mes*PCHPMes*}] (4 ), and the silylated analogue, Mes*PCHP(SiMe3 )Mes* (5 ), are reported. The aluminium complexes feature four‐membered PCPAl core structures consisting of diphosphaallyl ligands. The silylated phosphine5 was found to be a valuable precursor for the synthesis of4 as it cleanly reacts with the diaryl aluminium chloride [(C6 F5 )2 AlCl]2 . The aluminium complex3 reacts with molecular dihydrogen at room temperature under formation of the acyclic σ 2 λ 3, σ 3 λ 3 ‐diphosphine Mes*PCHP(H)Mes* and the corresponding dialkyl aluminium hydride [ t Bu2 AlH]3 . Thus, 3 belongs to the family of so‐called hidden frustrated Lewis pairs. Abstract : Hidden FLPs : Two aluminium diphosphamethanide complexes that feature four‐membered PCPAl core structures and diphosphaallyl ligands are presented. The aluminium complex [Al( t Bu)2 {Mes*PCHPMes*}] reacts with molecular dihydrogen at room temperature under formation of the acyclic diphosphine Mes*PCHP(H)Mes* (PH) and the corresponding dialkyl aluminium hydride [ t Bu2 AlH]3 (AlH; see figure).