Homo- and Heteroleptic Silylstannylenes: Synthesis, Structure and Use as Precursors to Bimetallic Compounds

Journal article

Two novel silyl-substituted stannylenes are reported: ArMesSn­{Si­(SiMe3)2(SitBuPh2)} (ArMes = 2,6-Mes2C6H3, Mes = 2,4,6-Me3C6H2) and Sn­{Si­(SiMe3)2(SitBuPh2)}2, the latter representing a very rare example of a homoleptic disilyl stannylene Together with the known stannylene ArMesSn­{Si­(SiMe3)3}, these systems are each shown to insert into the Au–Cl bond of (Ph3P)­AuCl to form complexes of the type (Ph3P)­Au­(SnR2Cl) containing four coordinate stannyl ligands (where R = aryl or silyl group). Similar behavior is shown toward (Cy3P)­AuI, yielding crystalline (Cy3P)­Au­{SnI­(ArMes)­(Si­(SiMe3)3)} in the case of ArMesSn­{Si­(SiMe3)3}. Subsequent iodide abstraction to yield [(Cy3P)­Au­{Sn­(ArMes)­(Si­(SiMe3)3)}]+ can be achieved using Li­[Al­(OR f )4] (R f = −C­(CF3)3), facilitated by the long tin–halide bond and strongly electron-donating tertiary phosphine ligand. This cationic complex represents the first structurally characterized example of a simple (two-coordinate) stannylene ligand bound to a gold center in a manner analogous to classical Au­(I) carbene complexes.

Authors: Murray, AJ; Wales, LL; Dietz, M; Poland, EM; McManus, C

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: American Chemical Society
• Journal: Organometallics
• Volume: 45
• Issue: 7
• Pages: 828-836
• Publication date: 2026-03-19
• Acceptance date: 2026-03-10
• DOI: 10.1021/acs.organomet.6c00001
• EISSN: 1520-6041
• ISSN: 0276-7333
• Language: English
• Keywords: Homoleptic; Bimetallic strip; Carbene; Phosphine; Yield (engineering); Cationic polymerization; Ligand (biochemistry)