000061429 001__ 61429
000061429 005__ 20200221144131.0
000061429 0247_ $$2doi$$a10.1021/acs.organomet.5b00777
000061429 0248_ $$2sideral$$a93638
000061429 037__ $$aART-2016-93638
000061429 041__ $$aeng
000061429 100__ $$aCasanova, N.
000061429 245__ $$aAmide-Directed Formation of Five-Coordinate Osmium Alkylidenes from Alkynes
000061429 260__ $$c2016
000061429 5060_ $$aAccess copy available to the general public$$fUnrestricted
000061429 5203_ $$aThe amide-directed synthesis of five-coordinate osmium alkylidene derivatives from alkynes is reported. These types of complexes, which have been elusive until now because of the tendency of osmium to give hydride alkylidyne species, are prepared by reaction of the dihydride OsH2Cl2(PiPr3)2 (1) with terminal alkynes containing a distal amide group. Complex 1 reacts with N-phenylhex-5-ynamide and N-phenylhepta-6-ynamide to give OsCl2{=C(CH3)(CH2)nNH(CO)Ph}(PiPr3)2 (n = 3 (2), 4 (3)). The relative position of carbonyl and NH groups in the organic substrates has no influence on the reaction. Thus, treatment of 1 with N-(pent-4-yn-1-yl)benzamide leads to OsCl2{=C(CH3)(CH2)3NHC(O)Ph}(PiPr3)2 (4). The new compounds are intermediate species in the cleavage of the C-C triple bond of the alkynes. Under mild conditions, they undergo the rupture of the Ca-CH3 bond of the alkylidene, which comes from the alkyne triple bond, to afford six-coordinate hydride-alkylidyne derivatives. In dichloromethane, complex 2 gives a 10:7 mixture of OsHCl2{=C(CH2)3C(O)NHPh}(PiPr3)2 (5) and OsHCl2{=CCH(CH3)(CH2)2C(O)NHPh}(PiPr3)2 (6). The first complex contains a linear separation between the alkylidyne Ca atom and the amide group, whereas the spacer is branched in the second complex. In contrast to the case for 2, complex 4 selectively affords OsHCl2{=C(CH2)3NHC(O)Ph}(PiPr3)2 (7). In spite of their instability, these compounds give the alkylidene-allene metathesis, being a useful entry to five-coordinate vinylidene complexes, including the dicarbon-disubstituted OsCl2(=C=CMe2)(PiPr3)2 (8) and the monosubstituted OsCl2(=C=CHCy)(PiPr3)2 (9).
000061429 536__ $$9info:eu-repo/grantAgreement/ES/MINECO/SAF2013-41943-R$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-52799-P$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-51912-REDC$$9info:eu-repo/grantAgreement/EC/FP7/340055/EU/Metal catalysis in biological habitats: New strategies for optical bio-sensing and targeted therapy/METBIOCAT$$9info:eu-repo/grantAgreement/ES/DGA/E35
000061429 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000061429 590__ $$a3.862$$b2016
000061429 591__ $$aCHEMISTRY, ORGANIC$$b12 / 59 = 0.203$$c2016$$dQ1$$eT1
000061429 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b8 / 46 = 0.174$$c2016$$dQ1$$eT1
000061429 592__ $$a1.723$$b2016
000061429 593__ $$aInorganic Chemistry$$c2016$$dQ1
000061429 593__ $$aPhysical and Theoretical Chemistry$$c2016$$dQ1
000061429 593__ $$aOrganic Chemistry$$c2016$$dQ1
000061429 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000061429 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, M. A.
000061429 700__ $$aGulías, M.
000061429 700__ $$0(orcid)0000-0002-6560-808X$$aLarramona, C.
000061429 700__ $$aMascareñas, J. L.
000061429 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, E.
000061429 773__ $$g35, 2 (2016), 91-99$$pOrganometallics$$tOrganometallics$$x0276-7333
000061429 8564_ $$s1581314$$uhttps://zaguan.unizar.es/record/61429/files/texto_completo.pdf$$yVersión publicada
000061429 8564_ $$s109932$$uhttps://zaguan.unizar.es/record/61429/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000061429 909CO $$ooai:zaguan.unizar.es:61429$$particulos$$pdriver
000061429 951__ $$a2020-02-21-13:04:44
000061429 980__ $$aARTICLE