000078338 001__ 78338
000078338 005__ 20191212100703.0
000078338 0247_ $$2doi$$a10.1021/acs.organomet.7b00906
000078338 0248_ $$2sideral$$a104903
000078338 037__ $$aART-2018-104903
000078338 041__ $$aeng
000078338 100__ $$0(orcid)0000-0002-3284-1053$$aBuil Juan, María Luisa$$uUniversidad de Zaragoza
000078338 245__ $$aOsmium Catalysts for Acceptorless and Base-Free Dehydrogenation of Alcohols and Amines: Unusual Coordination Modes of a BPI Anion
000078338 260__ $$c2018
000078338 5060_ $$aAccess copy available to the general public$$fUnrestricted
000078338 5203_ $$aA novel type of catalyst precursors for the dehydrogenation of hydrogen carriers based on organic liquids has been discovered. Complexes OsH6(PiPr3)2 (1) and OsH(OH)(CO)(PiPr3)2 (2) react with 1,3-bis(6'-methyl-2'-pyridylimino)isoindoline (HBMePI) to give OsH3{¿2-Npy,Nimine-(BMePI)}(PiPr3)2 (3) and OsH{¿2-Npy,Nimine-(BMePI)}(CO)(PiPr3)2 (4). The unprecedented ¿2-Npy,Nimine coordination mode of BMePI is thermodynamically preferred with Os(IV) and Os(II) metal fragments and allows for preparation of BMePI-based dinuclear metal cations. Treatment of OsH2Cl2(PiPr3)2 (5) with 0.5 equiv of HBMePI in the presence of KOtBu affords the chloride salt of the bis(osmium(IV)) dinuclear cation [{OsH3(PiPr3)2}2{µ-(¿2-Npy,Nimine)2-BMePI}]+ (6). Related homoleptic bis(osmium(II)) complexes have been also synthesized. Complex 4 reacts with the bis(solvento) [OsH(CO){¿1-O-[OCMe2]2}(PiPr3)2]BF4 to give [{OsH(CO)(PiPr3)2}2{µ-(¿2-Npy,Nimine)2-BMePI}]BF4 (7), whereas the addition of 0.5 equiv of HBMePI to {OsCl(¿6-C6H6)}2(µ–Cl)2 (8) affords [{OsCl(¿6-C6H6)}2{µ-(¿2-Npy,Nimine)2-BMePI}]Cl (9). The reactions of 4 with 8 and {OsCl(¿6-p-cymene)}2(µ–Cl)2 (10) lead to the heteroleptic cations [(PiPr3)2(CO)HOs{µ-(¿2-Npy,Nimine)2-BMePI}OsCl(¿6-arene)]+ (arene = C6H6 (11), p-cymene (12)). The electronic structrure and electrochemical properties of the dinuclear complexes were also studied. Complexes 3 and 4 are efficient catalyst precursors for the acceptorless and base-free dehydrogenation of secondary and primary alcohols and cyclic and lineal amines. The primary alcohols afford aldehydes. The amount of H2 released per gram of heterocycle depends upon the presence of a methyl group adjacent to the nitrogen atom, the position of the nitrogen atom in the heterocycle, and the size of the heterocycle.
000078338 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E35$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2016-81797-REDC$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-82935-P
000078338 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000078338 590__ $$a4.1$$b2018
000078338 591__ $$aCHEMISTRY, ORGANIC$$b11 / 57 = 0.193$$c2018$$dQ1$$eT1
000078338 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b5 / 45 = 0.111$$c2018$$dQ1$$eT1
000078338 592__ $$a1.473$$b2018
000078338 593__ $$aInorganic Chemistry$$c2018$$dQ1
000078338 593__ $$aPhysical and Theoretical Chemistry$$c2018$$dQ1
000078338 593__ $$aOrganic Chemistry$$c2018$$dQ1
000078338 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000078338 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, Miguel. A.
000078338 700__ $$0(orcid)0000-0001-8056-1083$$aGay, M. Pilar.
000078338 700__ $$aGómez-Gallego, Mar
000078338 700__ $$aNicasio A. I.
000078338 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, E.
000078338 700__ $$aSantiago, A.
000078338 700__ $$aSierra, Miguel A.
000078338 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000078338 773__ $$g37, 4 (2018), 603-617$$pOrganometallics$$tOrganometallics$$x0276-7333
000078338 8564_ $$s603944$$uhttps://zaguan.unizar.es/record/78338/files/texto_completo.pdf$$yPostprint
000078338 8564_ $$s102071$$uhttps://zaguan.unizar.es/record/78338/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000078338 909CO $$ooai:zaguan.unizar.es:78338$$particulos$$pdriver
000078338 951__ $$a2019-12-12-10:05:25
000078338 980__ $$aARTICLE