title: Copper-, palladium-, and platinum-containing complexes of an asymmetric dinucleating ligand.
abstract: The coordination chemistry of an asymmetric dinucleating hexadentate ligand LH(2) comprising neutral alkyltriamine and potentially dianionic dicarboxamido-pyridyl donor sets with copper, palladium, and platinum has been explored. Monometallic, dicopper, and heterodinuclear Cu-Pd and -Pt complexes have been prepared and characterized, including by NMR, EPR, UV-vis, and IR spectroscopy and X-ray crystallography. For example, the monometallic complexes [(LH(2))MCl]X (M = Cu, X = OTf; M = Pd or Pt, X = Cl) were prepared, wherein the metal(II) ions are coordinated to the triamine portion and the pyridyldicarboxamide is unperturbed. Treatment of LH(2) with [MesCu](x) (Mes = mesityl) provided a monocopper(I) complex, again with the metal coordinated only to the trialkylamine donor set. Reaction of [(LH(2))CuCl]OTf with NaOMe resulted in an unexpected migration of the copper(II)-chloride fragment to the pyridyldicarboxamide site to yield Na[LCuCl], from which a dicopper complex LCu(2)Cl(2) and mixed-metal complexes LCu(Cl)M(Cl) (M = Pd, Pt) were prepared by addition of CuCl(2) or MCl(2), respectively. The heterodinuclear complexes were also prepared by addition of CuCl(2) to [(LH(2))MCl]Cl.
authors.affiliation: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
authors.forename: Mohammad Reza
authors.initials: MR
authors.lastname: Halvagar
authors.forename: Benjamin
authors.initials: B
authors.lastname: Neisen
authors.forename: William B
authors.initials: WB
authors.lastname: Tolman
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D010984:Platinum / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization
chemical_list: D056831:Coordination Complexes; D008024:Ligands; D010984:Platinum; D010165:Palladium; D003300:Copper