000102072 001__ 102072
000102072 005__ 20210902121800.0
000102072 0247_ $$2doi$$a10.1021/acs.organomet.0c00156
000102072 0248_ $$2sideral$$a118247
000102072 037__ $$aART-2020-118247
000102072 041__ $$aeng
000102072 100__ $$0(orcid)0000-0003-0597-3357$$aCancela, L.$$uUniversidad de Zaragoza
000102072 245__ $$aOsmium- And Iridium-Promoted C-H Bond Activation of 2, 2'-Bipyridines and Related Heterocycles: Kinetic and Thermodynamic Preferences
000102072 260__ $$c2020
000102072 5060_ $$aAccess copy available to the general public$$fUnrestricted
000102072 5203_ $$aThe d2-hexahydride complex OsH6(PiPr3)2 (1) promotes the activation of C-H bonds of 2, 2'-bipyridines and related heterocycles. The study of the same reactions with the deuteride counterpart OsD6(PiPr3)2 (1-d) reveals that the activation of the C-H bonds situated in the sterically less hindered positions is kinetically preferred. However, the isolated products are the result of the thermodynamic control of the reactions. Thus, reactions of 1 with 2, 2'-bipyridine, 6-phenyl-2, 2'-bipyridine, and 6-methyl-2, 2'-bipyridine give the "rollover cyclometalation" products OsH3{¿2-C, N-[C5(R)H2N-py]}(PiPr3)2 (R = H (2), Ph (3), Me (4)), whereas 3, 5-dimethyl-6-phenyl-2, 2'-bipyridine affords OsH2{¿3-C, N, C-[C5H3N-(Me)2py-C5H4]}(PiPr3)2 (5), containing a dianionic C, N, C-pincer ligand. The behavior of substrates pyridyl-benzimidazolium and -imidazolium is similar. Reaction of 1 with 3-methyl-1-(6-phenylpyridin-2-yl)-1H-benzimidazolium tetrafluoroborate leads to OsH3{¿2-C, C-[MeBzim-C5(Ph)H2N]}(PiPr3)2 (6), bearing an anionic Cpy, CNHC-chelate. On the other hand, 3-methyl-1-(6-phenylpyridin-2-yl)-1H-imidazolium tetrafluoroborate yields [OsH2{¿3-C, N, C-(MeIm-py-C6H4)}(PiPr3)2]BF4 (7), containing a monoanionic C, N, C-pincer with a NHC-unit coordinated in an abnormal fashion. The reactivity pattern of these substrates is also observed with the d4-iridium-pentahydride IrH5(PiPr3)2 (8), which has generated IrH2{¿2-C, N-[C5(R)H2N-py]}(PiPr3)2 (R = H, (9), Ph (10)) and IrH{¿3-C, N, C-[C5H3N-(Me2)py-C5H4]}(PiPr3)2 (11). The osmium(IV)-carbon bonds display a higher degree of covalency than the iridium(III)-carbon bonds. In contrast to 2, the metalated carbon atom of 9 undergoes the addition of a proton of methanol to give [IrH2{¿2-N, N-(bipy)}(PiPr3)2]BF4 (12).
000102072 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E06-20R$$9info:eu-repo/grantAgreement/ES/DGA/FEDER$$9info:eu-repo/grantAgreement/ES/DGA/FSE$$9info:eu-repo/grantAgreement/ES/DGA/LMP148-18
000102072 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000102072 590__ $$a3.876$$b2020
000102072 591__ $$aCHEMISTRY, ORGANIC$$b13 / 57 = 0.228$$c2020$$dQ1$$eT1
000102072 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b11 / 45 = 0.244$$c2020$$dQ1$$eT1
000102072 592__ $$a1.231$$b2020
000102072 593__ $$aInorganic Chemistry$$c2020$$dQ1
000102072 593__ $$aPhysical and Theoretical Chemistry$$c2020$$dQ1
000102072 593__ $$aOrganic Chemistry$$c2020$$dQ1
000102072 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000102072 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, M.A.
000102072 700__ $$0(orcid)0000-0001-7183-4975$$aLópez, A.M.$$uUniversidad de Zaragoza
000102072 700__ $$0(orcid)0000-0003-0381-0917$$aOliván, M.
000102072 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, E.
000102072 700__ $$0(orcid)0000-0003-1709-3672$$aSan-Torcuato, A.
000102072 700__ $$0(orcid)0000-0003-1974-5507$$aVélez, A.$$uUniversidad de Zaragoza
000102072 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000102072 773__ $$g39, 11 (2020), 2102-2115$$pOrganometallics$$tOrganometallics$$x0276-7333
000102072 8564_ $$s2090877$$uhttps://zaguan.unizar.es/record/102072/files/texto_completo.pdf$$yPostprint
000102072 8564_ $$s2818127$$uhttps://zaguan.unizar.es/record/102072/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000102072 909CO $$ooai:zaguan.unizar.es:102072$$particulos$$pdriver
000102072 951__ $$a2021-09-02-09:54:12
000102072 980__ $$aARTICLE