Selective [2+1+1] Fragmentation of P4 by heteroleptic Metallasilylenes. Issue 41 (23rd June 2022)

• Record Type: Journal Article
• Authors: Schoening, Juliane; Gehlhaar, Alexander; Wölper, Christoph; Schulz, Stephan
• Is Part Of: Chemistry. Volume 28:Issue 41(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-06-23
• Subjects: P4 activation -- quantum chemical calculations -- silylene -- X-ray diffraction; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202201031
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Small‐molecule activation by low‐valent main‐group element compounds is of general interest. We here report the synthesis and characterization ( 1 H, 13 C, 29 Si NMR, IR, sc‐XRD) of heteroleptic metallasilylenes L 1 (Cl)MSiL 2 (M=Al 1, Ga 2, L 1 =HC[C(Me)NDipp]2, Dipp=2, 6‐ i Pr2 C6 H3 ; L 2 =PhC(N t Bu)2 ). Their electronic nature was analyzed by quantum chemical computations, while their promising potential in small‐molecule activation was demonstrated in reactions with P4, which occurred with unprecedented [2+1+1] fragmentation of the P4 tetrahedron and formation of L 1 (Cl)MPSi(L 2 )PPSi(L 2 )PM(Cl)L 1 (M=Al 3, Ga 4 ). Abstract : Si cuts in : Heteroleptic metallasilylenes L 1 (Cl)MSiL 2 (M=Al 1, Ga 2 ) react selectively with white phosphorus in a [2+1+1] fragmentation of the P4 tetrahedron to give L 1 (Cl)MPSi(L 2 )PPSi(L 2 )PM(Cl)L 1 (M=Al 3, Ga 4 ).