A New Cyclometalation Motif: Synthesis, Characterization, Structures, and Reactivity of Pallada- and Platinacycles with a Bidentate {C(sp2,cyrhetrene),N}− Ligand

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,...

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Detalhes bibliográficos
Autores: Cautivo, Teresa, Klahn, Hugo, Godoy, Fernando, López Martínez, Ma. Concepción, Font Bardia, Ma. Mercedes, Calvet Pallàs, Maria Teresa, Gutierrez-Puebla, Enrique, Monge, Angeles
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2011
País:España
Recursos:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/214402
Acesso em linha:https://hdl.handle.net/2445/214402
Access Level:acceso abierto
Palavra-chave:Pal·ladi (Element químic)
Lligands
Platí
Estructura cristal·lina (Sòlids)
Palladium
Ligands
Platinum
Layer structure (Solids)
Descrição
Resumo: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.

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