Abstract
We describe the first experimental example of a theoretically predicted Frustrated Lewis Trio (FLT). A tetradentate PNNP ligand is used to stabilise a highly electrophilic [TiCl3]+ fragment in a way that results in two equally long and frustrated Ti-P bonds. A combined experimental and computational approach revealed a distinct role of each Lewis basic phosphine in the heterolytic activation of chemical bonds. This dual functionality is characterised by a pendulum-like hemilability, where one of the phosphines acts as a nucleophile while the other serves as a hemilabile ligand that dynamically tunes the Ti-P distance as a function of the required electron density at the Ti centre.
| Original language | English |
|---|---|
| Pages (from-to) | 5555-5563 |
| Number of pages | 9 |
| Journal | Chemical Science |
| Volume | 15 |
| Issue number | 15 |
| Early online date | 8 Mar 2024 |
| DOIs | |
| Publication status | Published - 8 Mar 2024 |
Bibliographical note
Publisher Copyright:© 2024 The Royal Society of Chemistry.
Funding
We want to kindly acknowledge Roel Bienenmann for the fruitful discussions regarding the computational part of this work. Maartje Otten is kindly acknowledged for her help in designing the TOC. Prof. Dr Mu-Hyun (Mookie) Baik is kindly acknowledged for hosting D. L. J. B. in his group at KAIST, and for providing access to his computational infrastructure. This work was supported by The Netherlands Organization for Scientific Research (Grants 740.018.019 and OCENW.M20.016 to D. L. J. B). Part of this work also made use of the Dutch national e-infrastructure with the support of the SURF Cooperative using grants no. EINF-3520. The X-ray diffractometer has been financed by the Netherlands Organization for Scientific Research (NWO).
| Funders | Funder number |
|---|---|
| Nederlandse Organisatie voor Wetenschappelijk Onderzoek | OCENW.M20.016, 740.018.019 |
| Nederlandse Organisatie voor Wetenschappelijk Onderzoek | |
| SURF | EINF-3520 |