title: Synthesis, structure, and electronic properties of monomeric and dimeric trispyrazolylborate platinum(II) hydride complexes.
abstract: Tp'PtMe(H)2 (2) [Tp' = hydridotris(3,5-dimethylpyrazolyl)borate] has been prepared from Tp'PtMe(CO) (1) via reaction with water in a basic acetone/water mixture. Protonation of 2 at one of the pyrazole nitrogen atoms induces methane elimination, and the resulting platinum(II) monohydride solvent intermediate (3) can be trapped by added ligand. Two chiral cationic platinum(II) monohydride complexes of the type [kappa(2)-((Hpz)BHpz2)Pt(H)(L)][BAr'4] [L = MeCN (4), CH2=CH2 (5); pz = 3,5-dimethylpyrazolyl, BAr'4 = tetrakis(3,5-trifluoromethylphenyl)borate] have been isolated. If 2 is protonated in the absence of trapping ligand, a deep red hydride-bridged dinuclear complex, [kappa(2)-((Hpz)BHpz2)Pt(mu-H)]2[BAr'4]2 (6), forms. DFT calculations supplement intuitive expectations regarding 3-center-2-electron bridging orbital descriptions for the electronic structure of this complex. X-ray structure determinations for the monomeric acetonitrile adduct 4 and the dicationic dimer 6 are reported.
authors.affiliation: Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, USA.
authors.forename: S
authors.initials: S
authors.lastname: Reinartz
authors.forename: M H
authors.initials: MH
authors.lastname: Baik
authors.forename: P S
authors.initials: PS
authors.lastname: White
authors.forename: M
authors.initials: M
authors.lastname: Brookhart
authors.forename: J L
authors.initials: JL
authors.lastname: Templeton
mesh_terms: D001896:Boron Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D018360:Crystallography, X-Ray; D019281:Dimerization; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009944:Organoplatinum Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D011720:Pyrazoles / Q000138:chemical synthesis* / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet
chemical_list: D001896:Boron Compounds; D008024:Ligands; D009944:Organoplatinum Compounds; D011720:Pyrazoles