Syntheses, Reactivities, Characterization, and Crystal Structures of Dipalladium Complexes Containing the 1,3-pyrimidinyl Ligand: Structures of [Pd(PPh)(Br)](μ,η-CHN), [Pd(Br)](μ,η-Hdppa), and [{Pd(PPh)(CHCN)}(μ,η-CHN)][BF].

In a refluxing chloroform solutionthe η-pyrimidinyl {pyrimidinyl = CHN} palladium complex [Pd(PPh)(η-CHN)(Br)],exhibited intermolecular displacement of two triphenylphosphine ligands to form the doubly bridged η-pyrimidinyl Dipalladium complex [Pd(PPh)(Br)](μ,η-CHN),. The treatment ofwith Hdppa {Hdppa =,-bisdiphenyl phosphinoamine} in refluxing dichloromethane yielded the doubly bridged Hdppa dipalladium complex [Pd(Br)](μ,η-Hdppa),. Complexreacted with the bidentate ligand, NHSCNCHand, NaSCOEt, and the tridentate ligand, KTp {Tp = tris(pyrazoyl-1-yl)borate}, to form the η-dithio η-pyrimidinyl complex [Pd(PPh)(η-CHN)(η-SS)], (: SS = SCNCH;: SS = SCOEt) and η-Tp η-pyrimidinyl complex [Pd(PPh)(η-CHN)(η-Tp)],, respectively. Treatment ofwith AgBFin acetonitrile at room temperature resulted in the formation of the doubly bridged η-pyrimidinyl dipalladium complex [{Pd(PPh)(CHCN)}(μ,η-CHN)][BF],. All of the complexes were identified using spectroscopic methods, and complexes,, andwere determined using single-crystal X-ray diffraction analyses.