Stannylene Ambiphilicity Enables Formation of a Trimetallic Complex
5 affiliations
- 1Institut für Anorganische Chemie, Georg-August-Universität Göttingen, Tammannstraße 4, Göttingen, Germany, D-37077
- 2Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, Göttingen, Germany, D-37077
- 3Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, Berlin, Germany, D-12489
- 4Department of Chemistry
- 5University of Manchester
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.
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BibTeX
@misc{kieselbach2026stannylene,
title = {{Stannylene Ambiphilicity Enables Formation of a Trimetallic Complex}},
author = {Jonathan Kieselbach and Christopher Golz and Jasmin Alsadi and Josh Abbenseth and Malte Fischer},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008877/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008877/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Stannylene Ambiphilicity Enables Formation of a Trimetallic Complex
AU - Jonathan Kieselbach
AU - Christopher Golz
AU - Jasmin Alsadi
AU - Josh Abbenseth
AU - Malte Fischer
PY - 2026
DA - 2026/09/15
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008877/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008877/v1
AB - 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.
ER -