78338 20191212100703.0 doi 10.1021/acs.organomet.7b00906 sideral 104903 ART-2018-104903 eng (orcid)0000-0002-3284-1053 Buil Juan, María Luisa Universidad de Zaragoza Osmium Catalysts for Acceptorless and Base-Free Dehydrogenation of Alcohols and Amines: Unusual Coordination Modes of a BPI Anion 2018 Access copy available to the general public Unrestricted A 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. info:eu-repo/grantAgreement/ES/DGA/E35 info:eu-repo/grantAgreement/ES/MINECO/CTQ2016-81797-REDC info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-82935-P info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 4.1 2018 CHEMISTRY, ORGANIC 11 / 57 = 0.193 2018 Q1 T1 CHEMISTRY, INORGANIC & NUCLEAR 5 / 45 = 0.111 2018 Q1 T1 1.473 2018 Inorganic Chemistry 2018 Q1 Physical and Theoretical Chemistry 2018 Q1 Organic Chemistry 2018 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion (orcid)0000-0002-4829-7590 Esteruelas, Miguel. A. (orcid)0000-0001-8056-1083 Gay, M. Pilar. Gómez-Gallego, Mar Nicasio A. I. (orcid)0000-0003-2094-719X Oñate, E. Santiago, A. Sierra, Miguel A. 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 37, 4 (2018), 603-617 Organometallics Organometallics 0276-7333 603944 http://zaguan.unizar.es/record/78338/files/texto_completo.pdf Postprint 102071 http://zaguan.unizar.es/record/78338/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:78338 articulos driver 2019-12-12-10:05:25 ARTICLE