A tour in the chemistry of a tricoordinate Rh(−I) complex

Varela-Izquierdo, Víctor ; López, José A. (Universidad de Zaragoza) ; Ciriano, Miguel A. ; Tejel, Cristina

Resumen: The 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.

Idioma: Inglés

DOI: 10.1002/chem.202501877

Año: 2025

Publicado en: Chemistry - A European Journal (2025), e202501877 [9 pp.]
ISSN: 0947-6539

Financiación: info:eu-repo/grantAgreement/ES/AEI/PID2020-119512GB-I00
Financiación: info:eu-repo/grantAgreement/ES/AEI/PID2023-148472NB-I00
Financiación: info:eu-repo/grantAgreement/ES/DGA/E50-23R
Financiación: info:eu-repo/grantAgreement/ES/MICINN/RED2022-134074-T

Tipo y forma: Article (Published version)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)