doi:10.1002/ejic.202100399engGaliana-Cameo M.Passarelli V.Pérez-Torrente J.J.Di Giuseppe A.Castarlenas R.Variation on the p-acceptor ligand within a Rhi-N-Heterocyclic carbene framework: divergent catalytic outcomes for phenylacetylene-methanol transformationsART-2021-127067A series of neutral and cationic rhodium complexes bearing IPr {IPr=1, 3-bis-(2, 6-diisopropylphenyl)imidazolin-2-carbene} and p-acceptor ligands are reported. Cationic species [Rh(¿4-cod)(IPr)(NCCH3)]+ and [Rh(CO)(IPr)(L)2]+ (L=pyridine, CH3CN) were obtained by chlorido abstraction in suitable complexes, whereas the cod-CO derivative [Rh(¿4-cod)(IPr)(CO)]+ was formed by the carbonylation of [Rh(¿4-cod)(IPr)(NCCH3)]+. Alternatively, neutral derivatives of type RhCl(IPr)(L)2 {L=tBuNC or P(OMe)3} can be accessed from [Rh(µ-Cl)(¿2-coe)(IPr)]2. In addition, the mononuclear species Rh(CN)(¿4-cod)(IPr) was prepared by cyanide-chlorido anion exchange, which after carbonylation afforded the unusual trinuclear compound [Rh{1¿C, 2¿N-(CN)}(CO)(IPr)]3. Divergent catalytic outcomes in the phenylacetylene-methanol transformations have been observed. Thus, enol ethers, arisen from hydroalkoxylation of the alkyne, were obtained with neutral Rh-CO catalyst precursors whereas dienol ethers were formed with cationic catalysts. Variable amounts of alkyne dimerization, cyclotrimerization or polymerization products were obtained in the absence of a strong p-acceptor ligand on the catalyst. © 2021 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH2021http://zaguan.unizar.es/record/11737510.1002/ejic.202100399http://zaguan.unizar.es/record/117375oai:zaguan.unizar.es:117375info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20Rinfo:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00info:eu-repo/grantAgreement/ES/MINECO/IJCI-2015-27029European Journal of Inorganic Chemistry 2021, 29 (2021), 2947-2957by-nc-ndhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/info:eu-repo/semantics/openAccess