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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
Synthesis, structure, and electronic properties of monomeric and dimeric trispyrazolylborate platinum(II) hydride
S Reinartz1, M H Baik, P S White
1Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, USA.
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.
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