Selective [2+1+1] Fragmentation of P4 by heteroleptic Metallasilylenes

Chemistry. 2022 Jul 20;28(41):e202201031. doi: 10.1002/chem.202201031. Epub 2022 Jun 23.

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 L1 (Cl)MSiL2 (M=Al 1, Ga 2, L1 =HC[C(Me)NDipp]2 , Dipp=2,6-i Pr2 C6 H3 ; L2 =PhC(Nt 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 L1 (Cl)MPSi(L2 )PPSi(L2 )PM(Cl)L1 (M=Al 3, Ga 4).

Keywords: P4 activation; X-ray diffraction; quantum chemical calculations; silylene.