151473 20251017144619.0 doi 10.1039/d1dt00597a sideral 126632 ART-2021-126632 eng Pérez-Bitrián A. (orcid)0000-0003-2260-676X Hydrogen bonding to metals as a probe for an inverted ligand field 2021 Access copy available to the general public Unrestricted Electron-rich, late transition metals are known to act as hydrogen-bonding (HBd) acceptors. In this regard, Pt(ii) centres in square-planar environments are particularly efficient. It is however puzzling that no convincing experimental evidence is currently available for the isoelectronic neighbour Au(iii) being involved in HBd interactions. We report now on the synthesis and characterisation of two series of isoleptic and isoelectronic (d8) compounds [(CF3)3Pt(L)]-and (CF3)3Au(L), where the L ligands are based on the quinoline frame and have been selected to favour HBd with the metal centre. Strong HBd interactions were actually found in the Pt(ii) compounds, based on structural and spectroscopic evidence, and they were further confirmed by theoretical calculations. In contrast, no evidence was obtained in the Au(iii) case. In order to find the reason underlying this general disparity, we undertook a detailed theoretical analysis of the model systems [(CF3)3Pt(py)]-and (CF3)3Au(py). This study revealed that the filled dz2orbital is the HOMO in the case of Pt(ii), but is buried in the lower energy levels in the case of Au(iii). The sharply different electronic configurations involve ligand-field inversion on going from Pt to the next element Au. This is not a gradual but an abrupt change, which invalidates Au(iii) as a HBd-acceptor wherever ligand-field inversion occurs. info:eu-repo/grantAgreement/ES/DGA/E17-20R info:eu-repo/grantAgreement/ES/MECD/FPU15-03940 info:eu-repo/grantAgreement/ES/MICIU-FEDER/PGC2018-094749-B-I00 info:eu-repo/semantics/openAccess by-nc https://creativecommons.org/licenses/by-nc/4.0/deed.es 4.569 2021 CHEMISTRY, INORGANIC & NUCLEAR 7 / 46 = 0.152 2021 Q1 T1 0.864 2021 Inorganic Chemistry 2021 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Baya M. Universidad de Zaragoza (orcid)0000-0002-2492-625X Casas J.M. Universidad de Zaragoza (orcid)0000-0003-0341-7699 Martín A. (orcid)0000-0002-4808-574X Menjón B. (orcid)0000-0001-9045-5102 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 50, 16 (2021), 5465-5472 Dalton Trans. Dalton Transactions 1477-9226 1374800 http://zaguan.unizar.es/record/151473/files/texto_completo.pdf Versión publicada 2658002 http://zaguan.unizar.es/record/151473/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:151473 articulos driver 2025-10-17-14:20:57 ARTICLE