000150533 001__ 150533
000150533 005__ 20250210102457.0
000150533 0247_ $$2doi$$a10.1021/acs.inorgchem.4c02652
000150533 0248_ $$2sideral$$a140342
000150533 037__ $$aART-2024-140342
000150533 041__ $$aeng
000150533 100__ $$aVidondo, Javier$$uUniversidad de Zaragoza
000150533 245__ $$aProtonation of Dppbz- and Binap-Ligated Rhodathiaboranes Yielding Hydron, Hydride, and Hydrogen Exchange
000150533 260__ $$c2024
000150533 5060_ $$aAccess copy available to the general public$$fUnrestricted
000150533 5203_ $$aThe reaction of the 11-vertex rhodathiaborane [8,8,8-(H)(PPh3)2-3-(NC5H5)-nido-7,8-RhSB9H10] (1) with 1,2-bis(diphenylphosphine)benzene (dppbz) and (S)-(−)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (binap) affords [1,1-(η2-dppbz)-3-(NC5H5)-closo-1,2-RhSB9H8] (2) and [1,1-(η2-binap)-3-(NC5H5)-closo-1,2-RhSB9H8] (3). These 11-vertex closo-rhodathiaborane chelates result from PPh3 ligand substitution at the rhodium center and a nido-to-closo structural cluster transformation driven by H2 loss. Treating compounds 2 and 3 with triflic acid (TfOH) leads to the formation of cationic clusters 4 and 5. The hydrons bind to the polyhedral clusters, acquiring hydride character and providing chemical nonrigidity that manifests through metal vertex-to-thiaborane pseudo-rotations and concomitant hydron tautomerisms. The resulting cations react with hydrogen to form mixtures of hydrons, hydrogen, and hydridorhodathiaboranes in equilibrium. The reaction products are the result of heterolytic cleavage of the H–H bond, with full participation of the clusters and the addition of hydrogen atoms to the cages. In these reactions, there is a conversion of electrons and hydrons into hydrogen, and hydrogen into hydride ligands, demonstrating that these boron-based metal compounds act as electron reservoirs, capable of promoting multielectron processes.
000150533 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E05-23R$$9info:eu-repo/grantAgreement/ES/MCIU-AEI-FEDER/PID2021-122406NB-I00
000150533 540__ $$9info:eu-repo/semantics/embargoedAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000150533 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000150533 700__ $$aUrdániz, Laura
000150533 700__ $$0(orcid)0000-0002-8220-6031$$aSanz Miguel, Pablo J.$$uUniversidad de Zaragoza
000150533 700__ $$0(orcid)0000-0002-8845-0174$$aRodríguez, Ricardo
000150533 700__ $$0(orcid)0000-0003-2299-9428$$aMacías, Ramón$$uUniversidad de Zaragoza
000150533 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000150533 773__ $$g63, 42 (2024), 19593-19606$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669
000150533 8564_ $$s1410101$$uhttps://zaguan.unizar.es/record/150533/files/texto_completo.pdf$$yPostprint$$zinfo:eu-repo/date/embargoEnd/2025-10-08
000150533 8564_ $$s2808012$$uhttps://zaguan.unizar.es/record/150533/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint$$zinfo:eu-repo/date/embargoEnd/2025-10-08
000150533 909CO $$ooai:zaguan.unizar.es:150533$$particulos$$pdriver
000150533 951__ $$a2025-02-10-08:27:47
000150533 980__ $$aARTICLE