118825 20240319081007.0 doi 10.1021/acs.inorgchem.2c01441 sideral 130025 ART-2022-130025 eng Arnal Vallés, L. Universidad de Zaragoza (orcid)0000-0002-0283-9307 High-Valent Pyrazolate-Bridged Platinum Complexes: A Joint Experimental and Theoretical Study 2022 Access copy available to the general public Unrestricted Complexes {Pt(C^C*)(µ-pz)}2] (HC^C*A= 1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1H-imidazol-2-ylidene 1a, HC^C*B= 1-phenyl-3-methyl-1H-imidazol-2-ylidene 1b) react with methyl iodide (MeI) at room temperature in the dark to give compounds {PtIV(C^C*)Me(µ-pz)}2(µ-I)]I (C^C*A2a, C^C*B2b). The reaction of 1a with benzyl bromide (BnBr) in the same conditions afforded Br(C^C*A)PtIII(µ-pz)2PtIII(C^C*A)Bn] (5a), which by heating in BnBr(l) became {PtIV(C^C*A)Bn(µ-pz)}2(µ-Br)]Br (6a). Experimental investigations and density functional theory (DFT) calculations on the mechanisms of these reactions from 1a revealed that they follow a SN2 pathway in the two steps of the double oxidative addition (OA). Based on the DFT investigations, species such as (C^C*A)PtIII(µ-pz)2PtIII(C^C*A)R]X (RX = MeI Int-Me, BnBr Int-Bn) and (C^C*A)PtII(µ-pz)2PtIV(C^C*A)(R)X] (RX = MeI Int'-Me, BnBr Int'-Bn) were proposed as intermediates for the first and the second OA reactions, respectively. In order to put the mechanisms on firmer grounds, Int-Me was prepared as (C^C*A)PtIII(µ-pz)2PtIII(C^C*A)Me]BF4(3a') and used to get I(C^C*A)PtIII(µ-pz)2PtIII(C^C*A)Me](4a), (C^C*A)PtII(µ-pz)2PtIV(C^C*A)(Me)I](Int'-Me), and {PtIV(C^C*)Me(µ-pz)}2(µ-I)]BF4(2a'). The single-crystal X-ray structures of 2a, 2b, 3a', and 5a along with the mono- and bi-dimensional 1H and 195Pt{1H} NMR spectra of all the named species allowed us to compare structural and spectroscopic data for high-valent complexes with the same core {Pt(C^C*)(µ-pz)}2] but different oxidation states. © 2022 American Chemical Society. All rights reserved. info:eu-repo/grantAgreement/ES/DGA/E17-20R info:eu-repo/grantAgreement/ES/MICIU-FEDER/PGC2018-094749-B-I00 info:eu-repo/semantics/openAccess by http://creativecommons.org/licenses/by/3.0/es/ 4.6 2022 CHEMISTRY, INORGANIC & NUCLEAR 5 / 42 = 0.119 2022 Q1 T1 0.997 2022 Chemistry (miscellaneous) 2022 Q1 Physical and Theoretical Chemistry 2022 Q1 Inorganic Chemistry 2022 Q1 8.0 2022 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Escudero, D. Fuertes Lorda, S. (orcid)0000-0003-1812-3175 Martin, A. Sicilia Martínez, V. Universidad de Zaragoza (orcid)0000-0002-0257-0483 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 61, 32 (2022), 12559-12569 Inorg. chem. Inorganic Chemistry 0020-1669 4780595 http://zaguan.unizar.es/record/118825/files/texto_completo.pdf Versión publicada 3201451 http://zaguan.unizar.es/record/118825/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:118825 articulos driver 2024-03-18-14:45:04 ARTICLE