000160967 001__ 160967
000160967 005__ 20251017144553.0
000160967 0247_ $$2doi$$a10.1021/acs.inorgchem.5c00332
000160967 0248_ $$2sideral$$a144203
000160967 037__ $$aART-2025-144203
000160967 041__ $$aeng
000160967 100__ $$aFerrer-Bru, Carlos
000160967 245__ $$aActivation of CO, Isocyanides, and Alkynes by frustrated Lewis Pairs based on Cp*M/N (M = Rh, Ir) Couples
000160967 260__ $$c2025
000160967 5060_ $$aAccess copy available to the general public$$fUnrestricted
000160967 5203_ $$aThe complexes [Cp*M(κ3N,N′,N″-L)][SbF6] (Cp* = η5-C5Me5; M = Rh, 1, Ir, 2; HL = pyridinyl-amidine) display M/N transition metal frustrated Lewis pair reactivity toward a range of substrates containing triple bonds. Whereas the rhodium complex 1 reacts with CO yielding compound [Cp*Rh(CO)(κ2C,N-LCO)][SbF6] (3), which contains a terminal carbonyl and a carbamoyl group, the iridium complex 2 generates compound [Cp*Ir(κ3C,N,N′-LCO)][SbF6] (4), which only features the carbamoyl group. Compounds 1 and 2 react with stoichiometric amounts of the isocyanides CNR (R = Cyclohexyl, p-C6H4(OMe), CH2SO2(p-Tolyl)) to give the corresponding 1,1-insertion complexes [Cp*M(κ3C,N,N′-LCNR)][SbF6] (5–10). Complexes containing inserted and coordinated isocyanide ligands of formula [Cp*M(CNR)(κ2C,N-LCNR)][SbF6] (11–15) are obtained upon treating 1 and 2 with excess of the corresponding isocyanide. Compound 2 reacts with CNtBu affording the adduct [Cp*Ir(CNtBu)(κ2N,N′-L)][SbF6] (16) which contains a terminal CNtBu ligand. Complex 16 is protonated by HSbF6 to give [Cp*Ir(CNtBu)(κ2N,N′-HL)][SbF6]2 (17). The terminal alkynes HC≡CR (R = Ph, CO2Et) react with 1 and 2 rendering the alkynyl complexes 18–21. Dimethyl acetylenedicarboxylate reacts with complex 2 to give compound 22 via the formal 1,2-addition of a basic nitrogen atom and the metal across the alkyne triple bond. The new complexes have been characterized by analytical, spectroscopic and X-ray diffraction (XRD) methods.
000160967 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E05-23R$$9info:eu-repo/grantAgreement/ES/MCIU-AEI-FEDER/PID2021-122406NB-I00$$9info:eu-repo/grantAgreement/ES/MCIU/CTQ2018-095561-BI00
000160967 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttps://creativecommons.org/licenses/by/4.0/deed.es
000160967 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000160967 700__ $$0(orcid)0000-0003-4568-2204$$aFerrer, Joaquina$$uUniversidad de Zaragoza
000160967 700__ $$0(orcid)0000-0001-8054-2237$$aLahoz, Fernando J.
000160967 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, Pilar
000160967 700__ $$0(orcid)0000-0003-4196-5856$$aCarmona, Daniel
000160967 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000160967 773__ $$g64, 21 (2025), 10435-10451$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669
000160967 8564_ $$s4421813$$uhttps://zaguan.unizar.es/record/160967/files/texto_completo.pdf$$yVersión publicada
000160967 8564_ $$s3267799$$uhttps://zaguan.unizar.es/record/160967/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000160967 909CO $$ooai:zaguan.unizar.es:160967$$particulos$$pdriver
000160967 951__ $$a2025-10-17-14:12:19
000160967 980__ $$aARTICLE