Cyclopalladated complexes derived from benzamidoxime
Antonio Abellán-López1, María-Teresa Chicote, Delia Bautista
1Grupo de Química Organometálica, Departamento de Química Inorgánica, Facultad de Química, Universidad de Murcia, Apartado 4021, 30071 Murcia, Spain. antabelo@um.es mch@um.es jvs1@um.es.
Abstract:
Cyclopalladated benzamidoxime complexes [Pd{C,N-C6H4{C(NH2)[double bond, length as m-dash]NOH}-2}Cl(L)] (L = PTol3, Tol = C6H4Me-4 (); XyNC, Xy = C6H3Me2-2,6 (); pic, C5H4Me-4 ()), [Pd{C,N-C6H4{C(NH2)[double bond, length as m-dash]NOH}-2}(L2)]ClO4 (L = pic (); L2 = 4,4'-di-tert-butyl-2,2'-bipyridine, tbbpy ()) and PPN[Pd{C,N-C6H4{C(NH2)[double bond, length as m-dash]NOH}-2}Cl2] () are prepared by reacting [Pd{C,N-C6H4{C(NH2)[double bond, length as m-dash]NOH}-2}(μ-Cl)]2 () with the appropriate neutral ligand or with [PPN]Cl, respectively. The cationic complexes are obtained in the presence of NaClO4. The reaction of with K(t)BuO affords the dinuclear oximato complex [Pd{μ-C,N,O-C6H4{C(NH2)[double bond, length as m-dash]NO}-2}(PTol3)]2 () or, in the presence of ClCH2py·HCl, the pincer derivative [Pd{C,N,N'-C6H4{C(NH2)[double bond, length as m-dash]NOCH2(C5H4N-2)}-2}(PTol3)]ClO4 (). Complex reacts with XyNC to give the iminobenzoyl complex [Pd{C,N-C(N[double bond, length as m-dash]Xy)C6H4{C(NH2)[double bond, length as m-dash]NOH}-2}Cl(CNXy)] () resulting from the insertion of XyNC into the Pd-C bond. The dinuclear complex [{Pd(tbbpy)}2{C,N,N',O-C6H4{C(NH)[double bond, length as m-dash]NO}-2}]ClO4 () bearing a bridging tetradentate benzimido(oximate) ligand is obtained by reacting Pd(OAc)2 with tbbpy and the metal-ligand complex . The crystal structures of complexes , , and have been determined.
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