000079321 001__ 79321
000079321 005__ 20210618112019.0
000079321 0247_ $$2doi$$a10.1021/acs.organomet.8b00259
000079321 0248_ $$2sideral$$a107152
000079321 037__ $$aART-2018-107152
000079321 041__ $$aeng
000079321 100__ $$0(orcid)0000-0002-5296-6427$$aGalván Curto, S.$$uUniversidad de Zaragoza
000079321 245__ $$aß-Borylalkenyl Z- e Isomerization in Rhodium-Mediated Diboration of Nonfunctionalized Internal Alkynes
000079321 260__ $$c2018
000079321 5060_ $$aAccess copy available to the general public$$fUnrestricted
000079321 5203_ $$aThe elemental steps for the preparation of (E)-pinBC(Me)=C(Me)Bpin (Bpin = pinacolboryl) by means of the anti addition of B2pin2 to 2-butyne, promoted by the boryl complex Rh(Bpin){xant(PiPr2)2} (1; xant(PiPr2)2 = 9, 9-dimethyl-4, 5-bis(diisopropylphosphino)xanthene), have been analyzed from a kinetic point of view, and the intermediates of the process, the ß-borylakenyl complexes Rh{(Z)-C(Me)=C(Me)Bpin}{xant(PiPr2)2} (2) and Rh{(E)-C(Me)=C(Me)Bpin}{xant(PiPr2)2} (3), have been isolated and fully characterized. The key step for the formation of the diborylalkene is the transformation of 2 into 3 as a result of the Z-E isomerization of the ß-borylalkenyl group, which takes place via metallacyclopropene intermediates. The isomerization is sterically controlled, and the pincer diphosphine adapts its coordination mode to the requirements of the process happening to act as ¿2-P, P. The Z-E isomerization of the ß-borylalkenyl ligand of 2 is slower than the oxidative addition of the diborane to 1. As a consequence, under catalytic conditions, the formation of the syn-addition product (Z)-pinBC(Me)=C(Me)Bpin is favored, although the intermediate Rh(Bpin)3{xant(PiPr2)2} is much less stable than 2.
000079321 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E06-17R$$9info:eu-repo/grantAgreement/ES/DGA/FSE$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2016-81797-REDC$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-82935-P
000079321 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000079321 590__ $$a4.1$$b2018
000079321 591__ $$aCHEMISTRY, ORGANIC$$b11 / 57 = 0.193$$c2018$$dQ1$$eT1
000079321 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b5 / 45 = 0.111$$c2018$$dQ1$$eT1
000079321 592__ $$a1.473$$b2018
000079321 593__ $$aInorganic Chemistry$$c2018$$dQ1
000079321 593__ $$aPhysical and Theoretical Chemistry$$c2018$$dQ1
000079321 593__ $$aOrganic Chemistry$$c2018$$dQ1
000079321 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000079321 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, M.A.
000079321 700__ $$0(orcid)0000-0003-0381-0917$$aOliván, M.
000079321 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, E.
000079321 700__ $$0(orcid)0000-0003-1974-5507$$aVélez, A.
000079321 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000079321 773__ $$g37, 12 (2018), 1970-1978$$pOrganometallics$$tOrganometallics$$x0276-7333
000079321 8564_ $$s507978$$uhttps://zaguan.unizar.es/record/79321/files/texto_completo.pdf$$yPostprint
000079321 8564_ $$s110764$$uhttps://zaguan.unizar.es/record/79321/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000079321 909CO $$ooai:zaguan.unizar.es:79321$$particulos$$pdriver
000079321 951__ $$a2021-06-18-11:14:30
000079321 980__ $$aARTICLE