No Switching Cooperativity between Coordinated Azo Ligands on Complexes Having $M^{II}(phosphane-k^2P)\}^{2+}\ ( M = Pd, Pt)$ Scaffolds
A series of square-planar palladium and platinum compounds with cis-blocking phosphanes and terminal azobenzene ligands ${[M(dppp)-(azo)_{2}] (OTf)_{2} (azo = CN(C_{6}H_{4})-N = N-(C_{6}H_{4})CN (iso-cyano), CN(C_{6}H_{4})-N = N-(C_{6}H_{5}) (iso-Ph)) and [{M_{2}(tpbz)}(azo)_{4}](OTf)_{4}(azo = CN(C...
| Autores: | , , , , |
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| Tipo de documento: | artigo |
| Estado: | Versão publicada |
| Data de publicação: | 2024 |
| País: | España |
| Recursos: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositório: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:dnet:recercat____::81382c4d12a2a4b8da3b5108ef60a8c0 |
| Acesso em linha: | https://hdl.handle.net/2445/228570 |
| Access Level: | Acceso aberto |
| Palavra-chave: | Lligands Pal·ladi (Element químic) Dissolvents Platí Ligands Palladium Solvents Platinum |
| Resumo: | A series of square-planar palladium and platinum compounds with cis-blocking phosphanes and terminal azobenzene ligands ${[M(dppp)-(azo)_{2}] (OTf)_{2} (azo = CN(C_{6}H_{4})-N = N-(C_{6}H_{4})CN (iso-cyano), CN(C_{6}H_{4})-N = N-(C_{6}H_{5}) (iso-Ph)) and [{M_{2}(tpbz)}(azo)_{4}](OTf)_{4}(azo = CN(C_{6}H_{4})-N = N-(C_{6}H_{5})}$ have been synthesized and fully characterised. Similarly to the uncoordinated ligands, the new coordination compounds have shown to be photochemically active with respect to their trans-to-cis isomerization process. Their cis-to-trans back spontaneous reaction have been studied as a function of solvent, temperature and pressure and the corresponding activation parameters determined in order to investigate the mechanism of these transformations. The results obtained are indicative of the operation of a rotational mechanism with no cooperativity between the azo ligands attached to the same metal. DFT calculations have been carried out in order to estimate the relative energies of the different photoisomers for the theoretical interpretation of the experimental data. |
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