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oai:recercat.cat:2445/2144022025-11-19T20:55:38Zcom_2072_1057col_2072_478917col_2072_478923col_2072_478933

urn:hdl:2445/214402 A New Cyclometalation Motif: Synthesis, Characterization, Structures, and Reactivity of Pallada- and Platinacycles with a Bidentate {C(sp2,cyrhetrene),N}− Ligand Cautivo, Teresa Klahn, Hugo Godoy, Fernando López Martínez, Ma. Concepción Font Bardia, Ma. Mercedes Calvet Pallàs, Maria Teresa Gutierrez-Puebla, Enrique Monge, Angeles Pal·ladi (Element químic) Lligands Platí Estructura cristal·lina (Sòlids) Palladium Ligands Platinum Layer structure (Solids) The synthesis, characterization, X-ray crystal structure, and study of the reactivity of the novel cyretrenyl ligand [{(η5-C5H4-2-C5H4N)}Re(CO)3 (1) with Pd(OAc)2 or [MCl2(DMSO)2] (M = Pd, Pt) are reported. These studies have allowed us to obtain the bis-μ-ligand cyclopalladated complexes [Pd{[k2-C,N-(η5-C5H3)-2(C5H4N)]Re(CO)3)}(μ-X)]2 (X = OAc (2a), Cl (4a)) and monomeric pallada- and platinacycles of the general formula [M{[k2-C,N-(η5-C5H3)-2(C5H4N)]Re- (CO)3}(X)(L)] (M = Pd, L = PPh3, X = OAc (3a), Cl (5a); M = Pd, L = DMSO, X = Cl (6a); M = Pt, X = Cl, L = PPh3 (5b), DMSO (6b)), where compound 1 acts as a {C(sp2,cyrhetrene),N} bidentate ligand. All complexes were characterized by elemental analyses, infrared spectroscopy, and one- and twodimensional NMR. The X-ray crystal structures of 5a 3 1/2CH2Cl2, 5b, 6a 3CH2Cl2, and 6b confirm (a) the existence of the five-membered metallacycle, (b) the {C(sp2,cyrhetrene),N} mode of binding of the metallo ligand 1, and (c) the cis arrangement between the metalated carbon and the neutral L ligands (PPh3 or DMSO) in these products. A comparative study of the structures, spectroscopic properties, and reactivities of the new cyclometalated compounds and those of their analogues with a bidentate {C(sp2,ferrocene),N} ligand is also reported. 2024-07-05T11:42:08Z 2024-07-05T11:42:08Z 2011 2024-07-05T11:42:13Z info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Versió postprint del document publicat a: https://doi.org/10.1021/om200310r Organometallics, 2011, vol. 30, num.21, p. 5578-5589 https://doi.org/10.1021/om200310r (c) American Chemical Society, 2011 info:eu-repo/semantics/openAccess American Chemical Society Articles publicats en revistes (Química Inorgànica i Orgànica)