Abstract
Nickel carbenes are key reactive intermediates in the catalytic cyclopropanation of olefins and other reactions, but isolated examples are scarce and generally rely on low coordination numbers (≤3) to stabilize the metal−ligand multiple bond. Here we report the isolation and characterization of a stable tetracoordinated nickel carbene bearing a triphosphine pincer ligand. Its nucleophilic character is evidenced by reaction with acids, and it can transfer the carbene fragment to CO to form a ketene. A computational study of the Ni=C chemical bond sheds light on the role of the third phosphine in the pincer framework to the stabilization of the nickel carbene fragment.
| Original language | English |
|---|---|
| Article number | e202403211 |
| Pages (from-to) | 1-7 |
| Number of pages | 7 |
| Journal | Chemistry - A European Journal |
| Volume | 30 |
| Issue number | 68 |
| Early online date | 29 Aug 2024 |
| DOIs | |
| Publication status | Published - 5 Dec 2024 |
Bibliographical note
Publisher Copyright:© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.
Funding
The authors thank for financial support the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement No. 715060). P.M.P.-G. acknowledges funding from an ENW-XS grant (grant number: OCENW.XS21.4.038) from the Dutch Research Council (NWO). C.F.G. and P.V. acknowledge the Netherlands Organization for Scientific Research (NWO). This work made use of the Dutch national e-infrastructure with the support of the SURF Cooperative using grant no. EINF-3520. The authors thank for financial support the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement No. 715060). P.M.P.\u2010G. acknowledges funding from an ENW\u2010XS grant (grant number: OCENW.XS21.4.038) from the Dutch Research Council (NWO). C.F.G. and P.V. acknowledge the Netherlands Organization for Scientific Research (NWO). This work made use of the Dutch national e\u2010infrastructure with the support of the SURF Cooperative using grant no. EINF\u20103520.
| Funders | Funder number |
|---|---|
| European Research Council | |
| Horizon 2020 Framework Programme | 715060 |
| Horizon 2020 | OCENW.XS21.4.038 |
| SURF | EINF‐3520 |
| Not added | OCENW.XS21.4.038 |
Keywords
- bonding analysis
- carbene transfer
- metal carbenes
- metal-ligand multiple bonds
- nickel