Abstract
The polynuclear complex [{μ-C1,C4,N,N″-C(6)H(2){C(H)=N((n)Bu)}(2)-2,5}{Pd(μ-OAc)}](2) (I) reacts with tbbpy (4,4'-di-tert-butyl-2,2'-bipyridine) and TlOTf to form the dinuclear complex [{μ-C1,C4,N,N″-C(6)H(2){C(H)=N((n)Bu)}(2)-2,5}{Pd(tbbpy)}(2)] (1). The hydrolysis of I with acetic acid in a 5:1 acetone/water mixture, in the presence of two equivalents of tbbpy and excess NaX (X = Br, I), yields the dipalladated terephthalaldehyde complexes [C(6)H(2){PdX(tbbpy)}(2)-1,4-(CHO)(2)-2,5] [X = Br (2a), X = I (2b)], which are the first fully characterized complexes of this type. The reaction of 2a,b with CO results in the insertion of CO into both aryl-Pd bonds, forming [C(6)H(2){C(O){PdX(tbbpy)}}(2)-1,4-(CHO)(2)-2,5] [X = Br (3a), X = I (3b)], which are the first examples of complexes with CO inserted into two separate aryl-metal bonds involving the same ligand. The bromo complex 2a reacts with excess XylNC in acetone, causing the precipitation of the dinuclear complex 2,3,6,7-tetrahydrobenzo[1,2-c:4,5-c']dipyrrole-1,5-dione-2,6-dixylyl-3,7-bis{=C(NHXyl)-C(=NXyl)-[PdBr(CNXyl)(2)]} (4), which is the result of the insertion of three molecules of the isocyanide into each aryl-Pd bond and the nucleophilic attack of one of them at each formyl group. When complex 4 reacts with TlOTf and residual water in 1,2-dichloroethane at 70 °C, depalladation occurs, and the organic compound 2,3,6,7-tetrahydrobenzo[1,2-c:4,5-c']dipyrrole-1,5-dione-2,6-dixylyl-3,7-bis{=C(NHXyl)-C(O)NHXyl} (5) can be isolated. The crystal structures of 1·4CHCl(3), 4·2CH(2)Cl(2)·3hexane, and 5·2CDCl(3) have been determined by X-ray crystallography.