131298 20240207154753.0 doi 10.1039/d0dt02713h sideral 120565 ART-2020-120565 eng Parker, A. Half-sandwich complexes of osmium containing guanidine-derived ligands 2020 Pyridinyl- 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. Access copy available to the general public Unrestricted info:eu-repo/grantAgreement/ES/MICINN/CTQ2017-83421-P info:eu-repo/grantAgreement/ES/MICINN/CTQ2018-095561-BI00 info:eu-repo/grantAgreement/ES/MINECO/RYC-2013-13800 info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 4.39 2020 CHEMISTRY, INORGANIC & NUCLEAR 8 / 45 = 0.178 2020 Q1 T1 0.98 2020 Inorganic Chemistry 2020 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Lamata, P. Universidad de Zaragoza (orcid)0000-0001-9071-563X Viguri, F. Universidad de Zaragoza (orcid)0000-0002-6160-3046 Rodríguez, R. Universidad de Zaragoza (orcid)0000-0002-8845-0174 López, J.A. Universidad de Zaragoza (orcid)0000-0003-4500-1974 Lahoz, F.J. Universidad de Zaragoza (orcid)0000-0001-8054-2237 García-Orduña, P. Universidad de Zaragoza (orcid)0000-0002-7063-1292 Carmona, D. (orcid)0000-0003-4196-5856 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 49, 39 (2020), 13601-13617 Dalton Trans. Dalton Transactions 1477-9226 1927113 http://zaguan.unizar.es/record/131298/files/texto_completo.pdf Postprint 1415080 http://zaguan.unizar.es/record/131298/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:131298 articulos driver 2024-02-07-14:38:00 ARTICLE