000131298 001__ 131298
000131298 005__ 20240207154753.0
000131298 0247_ $$2doi$$a10.1039/d0dt02713h
000131298 0248_ $$2sideral$$a120565
000131298 037__ $$aART-2020-120565
000131298 041__ $$aeng
000131298 100__ $$aParker, A.
000131298 245__ $$aHalf-sandwich complexes of osmium containing guanidine-derived ligands
000131298 260__ $$c2020
000131298 5060_ $$aAccess copy available to the general public$$fUnrestricted
000131298 5203_ $$aPyridinyl- and phosphano-guanidino complexes of formula [(¿6-p-cymene)OsCl(H2L)][SbF6] (cymene = MeC6H4iPr; H2L = N, N'-bis(p-Tolyl)-N''-(2-pyridinylmethyl)guanidine, H2L1 (1) and N, N'-bis(p-Tolyl)-N''-(2-diphenylphosphanoethyl)guanidine, H2L2 (2)) have been prepared from the dimer [{(¿6-p-cymene)OsCl}2(µ-Cl)2] and H2L in the presence of NaSbF6. Treatment of complex 2 with HCl renders the phosphano-guanidinium complex [(¿6-p-cymene)OsCl2(H3L2)][SbF6] (3). Compounds 1 and 2 react with AgSbF6 rendering the cationic aqua complexes [(¿6-p-cymene)Os(H2L)(OH2)][SbF6]2 (H2L = H2L1 (4), H2L2 (5)). Addition of monodentate ligands L to compound 4 affords complexes of formula [(¿6-p-cymene)Os(H2L1)L][SbF6]2 (L = py (6), 4-(NHMe)py (7), CO (8), P(OMe)3 (9)). Treatment of complexes 4 and 5 with NaHCO3 renders the monocationic complexes [(¿6-p-cymene)Os(¿3N, N', N''-HL1)][SbF6] (10) and [(¿6-p-cymene)Os(¿3N, N', P-HL2)][SbF6] (11), respectively, in which the HL ligand adopts a fac-¿3 coordination mode. The new complexes have been characterised by analytical and spectroscopic means, including the determination of the crystal structures of the compounds 1-4, 6, 8, and 11, by X-ray diffractometric methods. The phosphano-guanidino complexes 2 and 5 exhibit a temperature dependent fluxional process in solution. The new 18 electron complexes 1, 2, 6, and 8-10 are active catalysts for the Friedel-Crafts reaction between trans-ß-nitrostyrene and N-methyl-2-methylindole. Conversions greater than 90% were obtained. Proton NMR studies support a mechanism involving the Brønsted-acid activation of trans-ß-nitrostyrene through the NH functionalities of the coordinated guanidine ligands.
000131298 536__ $$9info:eu-repo/grantAgreement/ES/MICINN/CTQ2017-83421-P$$9info:eu-repo/grantAgreement/ES/MICINN/CTQ2018-095561-BI00$$9info:eu-repo/grantAgreement/ES/MINECO/RYC-2013-13800
000131298 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000131298 590__ $$a4.39$$b2020
000131298 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b8 / 45 = 0.178$$c2020$$dQ1$$eT1
000131298 592__ $$a0.98$$b2020
000131298 593__ $$aInorganic Chemistry$$c2020$$dQ1
000131298 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000131298 700__ $$0(orcid)0000-0001-9071-563X$$aLamata, P.$$uUniversidad de Zaragoza
000131298 700__ $$0(orcid)0000-0002-6160-3046$$aViguri, F.$$uUniversidad de Zaragoza
000131298 700__ $$0(orcid)0000-0002-8845-0174$$aRodríguez, R.$$uUniversidad de Zaragoza
000131298 700__ $$0(orcid)0000-0003-4500-1974$$aLópez, J.A.$$uUniversidad de Zaragoza
000131298 700__ $$0(orcid)0000-0001-8054-2237$$aLahoz, F.J.$$uUniversidad de Zaragoza
000131298 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, P.$$uUniversidad de Zaragoza
000131298 700__ $$0(orcid)0000-0003-4196-5856$$aCarmona, D.
000131298 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000131298 773__ $$g49, 39 (2020), 13601-13617$$pDalton Trans.$$tDalton Transactions$$x1477-9226
000131298 8564_ $$s1927113$$uhttps://zaguan.unizar.es/record/131298/files/texto_completo.pdf$$yPostprint
000131298 8564_ $$s1415080$$uhttps://zaguan.unizar.es/record/131298/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000131298 909CO $$ooai:zaguan.unizar.es:131298$$particulos$$pdriver
000131298 951__ $$a2024-02-07-14:38:00
000131298 980__ $$aARTICLE