000161891 001__ 161891 000161891 005__ 20251017144629.0 000161891 0247_ $$2doi$$a10.1002/chem.202501877 000161891 0248_ $$2sideral$$a144538 000161891 037__ $$aART-2025-144538 000161891 041__ $$aeng 000161891 100__ $$0(orcid)0000-0002-7806-8959$$aVarela-Izquierdo, Víctor 000161891 245__ $$aA tour in the chemistry of a tricoordinate Rh(−I) complex 000161891 260__ $$c2025 000161891 5060_ $$aAccess copy available to the general public$$fUnrestricted 000161891 5203_ $$aThe finding of the unprecedented 16‐e tricoordinate planar rhodium(−Ι) complex, K[Rh(IPr)(dvtms)] (K[1]) (IPr = 1,3‐bis(2,6‐diisopropylphenyl)imidazolyl‐2‐ylidene, dvtms = divinyltretramethyldisiloxane) prompted us to explore its reactivity. K[1] reacts as a nucleophile with methyliodide to give [Rh(IPr)(dvtms)Me], a Rh(Ι) compound with an exceptional trigonal‐pyramidal structure. Other haloalkanes abstract one electron from K[1] to give the previously reported [Rh0(IPr)(dvtms)] complex. K[1] also reacts with protonic acids and weak proton sources such as water and ketones to eventually give the rare tricoordinate 14‐electron complex [RhI(IPr)(SiMe2OSiMe2CH = CH2)] with a Rh −Si bond. The 16‐electron complex [RhI(IPr)(SiMe2OSiMe2CH = CH2)(H2C = CH2)] was characterized as an intermediate in this reaction. Furthermore, K[1] runs up to five cycles of catalytic condensation of nonenolizable aldehydes to esters, such as p‐tolylaldehyde, before being fully converted into the inactive complex Rh(IPr)(η3‐C3H4ptolyl)(C2H4)] with fragmentation of the diolefin dvtms. Computational studies have provided valuable insights into the reactivity patterns and behavior of this complex, including those of the rhodium(−I)/rhodium(I) catalytic cycle. 000161891 536__ $$9info:eu-repo/grantAgreement/ES/AEI/PID2020-119512GB-I00$$9info:eu-repo/grantAgreement/ES/AEI/PID2023-148472NB-I00$$9info:eu-repo/grantAgreement/ES/DGA/E50-23R$$9info:eu-repo/grantAgreement/ES/MICINN/RED2022-134074-T 000161891 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttps://creativecommons.org/licenses/by/4.0/deed.es 000161891 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion 000161891 700__ $$0(orcid)0000-0003-4500-1974$$aLópez, José A.$$uUniversidad de Zaragoza 000161891 700__ $$0(orcid)0000-0002-7188-8014$$aCiriano, Miguel A. 000161891 700__ $$0(orcid)0000-0003-3306-0635$$aTejel, Cristina 000161891 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica 000161891 773__ $$g(2025), e202501877 [9 pp.]$$pChemistry (Weinh.)$$tChemistry - A European Journal$$x0947-6539 000161891 8564_ $$s1674554$$uhttps://zaguan.unizar.es/record/161891/files/texto_completo.pdf$$yVersión publicada 000161891 8564_ $$s3015085$$uhttps://zaguan.unizar.es/record/161891/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada 000161891 909CO $$ooai:zaguan.unizar.es:161891$$particulos$$pdriver 000161891 951__ $$a2025-10-17-14:25:37 000161891 980__ $$aARTICLE