Year: 2026
Type: article
Abstract: Low-valent heavier group 14 tetrylenes combine a stereochemically active lone pair with a vacant p-orbital at a single centre, resulting in a unique ambiphilic reactivity profile. However, exploiting these donor–acceptor properties to construct transition-metal complexes featuring bridging tetrylene units remains largely unexplored. Here we report a flexible pincer ligand in which an N,O,N pocket stabilises the monomeric stannylene [(PNONP)Sn] (Sn1) that itself presents a P,Sn,P pocket for nickel coordination and can be employed, either stepwise or in one pot, to afford the isolable NHC-stabilised tin–nickel heterobimetallics [(PNONP)SnNi(NHC)] Sn4a,b (NHC = N-heterocyclic carbene). Reaction of Sn4a with W(CO)6, envisaged as a simple test electrophile for the tin-centred lone pair, instead proceeds via unanticipated NHC-to-CO exchange and the resulting NHC-free tin–nickel-carbonyl fragment self-associates to give the dimeric complex [(PNONP)SnNi(CO)]2 (Sn5). Treatment of Sn4a with [(p-cymene)Ru(Cl)2]2 affords the target heterotrimetallic Ni–Sn–Ru complex [(PNONP)Sn{Ru(Cl)2(p-cyemene)}Ni(IiPr2Me2)] (Sn6), in which tin bridges the metal centres in a genuinely push–pull fashion, representing the first structurally authentification of such a bonding mode for a heavy tetrylene.
Source: Chemical Science
DOI: 10.1039/d6sc07102c
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: diamond
Awards: G1095617478, G787490620
OpenAlex ID: W7213276639