Small‐Molecule Activation by Heteroleptic Metallasilylenes. Issue 2 (7th November 2022)

• Record Type: Journal Article
• Authors: Schoening, Juliane; Wölper, Christoph; Schulz, Stephan
• Is Part Of: European journal of inorganic chemistry. Volume 26:Issue 2(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-11-07
• Subjects: Carbene homologues -- Main group elements -- C−C activation -- Oxidation -- X-ray diffraction; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.202200638
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: We report on reactions 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 ) with CO2, N2 O, and Me3 SiN3, yielding the corresponding carbonate complexes L 1 (Cl)MOSi(CO3 ‐κ 2 O, O−)L 2 (M=Al 3, Ga 4 ), silanoic esters L 1 (Cl)MOSi(O)L 2 (M=Al 5, Ga 6 ), and silaimine L 1 (Cl)GaSi(NSiMe3 )L 2 (8 ), whereas {L 2 Si[N(SiMe3 )Al(Cl)C(Me)NDipp][CHC(Me)N(Dipp)]} 7 was formed by C−C bond cleavage of the L 1 ligand. Compounds 3 –8 were characterized by NMR ( 1 H, 13 C) and IR spectroscopy, elemental analysis and single crystal X‐ray diffraction. Abstract : Heteroleptic metallasilylenes L 1 (Cl)MSiL 2 (M=Al 1, Ga 2 ) react with CO2 and N2 O with formation of oxygen‐bridged carbonate complexes and silanoic esters, whereas reactions with Me3 SiN3 gave the expected silaimine complex or occurred with unprecedented ring cleavage of the β ‐diketiminiate ligand.