2026-04-17T11:57:52Zhttps://recercat.cat/oai/request

oai:recercat.cat:2445/2285702026-04-08T13:36:48Zcom_2072_1057col_2072_478794col_2072_478905col_2072_478907col_2072_478917col_2072_478933

No Switching Cooperativity between Coordinated Azo Ligands on Complexes Having $M^{II}(phosphane-k^2P)\}^{2+}\ ( M = Pd, Pt)$ Scaffolds Raïch Panisello, Ot Jover Modrego, Jesús Puigjaner Vallet, Ma. Cristina Ferrer García, Montserrat Martínez López, Manuel, 1957- Lligands Pal·ladi (Element químic) Dissolvents Platí Ligands Palladium Solvents Platinum 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. 2026-03-27T11:39:05Z 2026-03-27T11:39:05Z 2024-08-21 2026-03-27T11:39:07Z info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion 0020-1669 https://hdl.handle.net/2445/228570 750062 eng Reproducció del document publicat a: https://doi.org/10.1021/acs.inorgchem.4c02169 Inorganic Chemistry, 2024, vol. 63, p. 16251-16263 https://doi.org/10.1021/acs.inorgchem.4c02169 cc by (c) Raïch Panisello, Ot et al., 2024 https://creativecommons.org/licenses/by/4.0/ info:eu-repo/semantics/openAccess 13 p. application/pdf American Chemical Society Articles publicats en revistes (Química Inorgànica i Orgànica)