000135907 001__ 135907
000135907 005__ 20250923084420.0
000135907 0247_ $$2doi$$a10.1021/acscatal.4c00264
000135907 0248_ $$2sideral$$a138905
000135907 037__ $$aART-2024-138905
000135907 041__ $$aeng
000135907 100__ $$0(orcid)0000-0001-9491-7167$$aHeras, Laura A. de las
000135907 245__ $$aHomo- and Cross-Coupling of Phenylacetylenes and a-Hydroxyacetylenes Catalyzed by a Square-Planar Rhodium Monohydride
000135907 260__ $$c2024
000135907 5060_ $$aAccess copy available to the general public$$fUnrestricted
000135907 5203_ $$aThe C–C triple bond of phenylacetylene undergoes the anti-Markovnikov addition of the Rh–H bond of RhH{κ3-P,O,P-[xant(PiPr2)2]} (1; xant(PiPr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) to give Rh{(E)–CH═CHPh}{κ3-P,O,P-[xant(PiPr2)2]} (2), which reacts with a second alkyne molecule to produce Rh(C≡CPh){κ3-P,O,P-[xant(PiPr2)2]} (3) and styrene before the transformation from 1 to 2 is complete. The metal center of 3 undergoes the oxidative addition of the C(sp)–H bond of another alkyne molecule to produce RhH(C≡CPh)2{κ3-P,O,P-[xant(PiPr2)2]} (4), which also reacts with more phenylacetylene before completing the transformation from 3 to 4. The reaction leads to Rh{(E)–CH═CHPh}(C≡CPh)2{κ3-P,O,P-[xant(PiPr2)2]} (5), which reductively eliminates (E)-1,4-diphenyl-1-buten-3-yne to regenerate 3. Complexes 3, 4, and 5 constitute a cycle for head-to-head dimerization of phenylacetylene. Consequently, complex 1 promotes the catalytic homocoupling of terminal alkynes to (E)-enynes, including the dimerization of α-hydroxyacetylenes to (E)-enyne-diols. The rate-determining step of the couplings depends on the nature of the alkyne, being the insertion of the C–C triple bond into the Rh–H bond of a bis(acetylide)-rhodium(III)-hydride intermediate for phenylacetylenes and the reductive elimination of the product (E)-enyne-diol for α-hydroxyacetylenes. In support of the latter, complex Rh{(E)–CH═CHC(OH)Ph2}{C≡CC(OH)Ph2}2{κ3-P,O,P-[xant(PiPr2)2]} (6) has been isolated and characterized by X-ray diffraction analysis. Complex 1 also effectively promotes the formation of compounds of the type (E)-5-phenyl-2-penten-4-yn-1-ol, by cross-coupling between phenylacetylenes and α-hydroxyacetylenes. These reactions take place through two cycles similar to the cycle that produces the homocouplings, the rate-determining step being the reductive elimination of (E)-enyn-ol for both. The catalytic performance of 1 provides good efficiency in homocoupling and cross-coupling reactions involving progestin-type compounds such as ethisterone.
000135907 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E06-23R$$9fo:eu-repo/grantAgreement/ES/DGA-FSE/LMP23-21$$9info:eu-repo/grantAgreement/ES/MCIN/AEI/10.13039/501100011033$$9info:eu-repo/grantAgreement/ES/MICINN/PID2020-115286GB-I00/AEI/10.13039/501100011033$$9info:eu-repo/grantAgreement/ES/MICINN/RED2022-134287-T
000135907 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000135907 590__ $$a13.1$$b2024
000135907 592__ $$a3.782$$b2024
000135907 591__ $$aCHEMISTRY, PHYSICAL$$b21 / 185 = 0.114$$c2024$$dQ1$$eT1
000135907 593__ $$aChemistry (miscellaneous)$$c2024$$dQ1
000135907 593__ $$aCatalysis$$c2024$$dQ1
000135907 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000135907 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, Miguel A.
000135907 700__ $$0(orcid)0000-0003-0381-0917$$aOliván, Montserrat
000135907 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, Enrique
000135907 773__ $$g14, 11 (2024), 8389-8404$$pACS catal.$$tACS CATALYSIS$$x2155-5435
000135907 8564_ $$s3311941$$uhttps://zaguan.unizar.es/record/135907/files/texto_completo.pdf$$yVersión publicada
000135907 8564_ $$s2817401$$uhttps://zaguan.unizar.es/record/135907/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000135907 909CO $$ooai:zaguan.unizar.es:135907$$particulos$$pdriver
000135907 951__ $$a2025-09-22-14:35:29
000135907 980__ $$aARTICLE