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DOI: 10.1039/A805432K (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 3335-3342

Heteropolymetallic compounds containing 1,1′-bis(diphenylphosphino)ferrocene (DPPF[hair space]) and pyrazolate ligands: synthesis, spectroscopic characterization and reactivity. Crystal and molecular structure of [(DPPF[hair space])Pt(az)2] [azH = pyrazole (pzH) or 3,5-dimethylpyrazole] and [(DPPF[hair space])Pt(µ-pz)2CdI2]

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Claudio Pettinari, Fabio Marchetti, Augusto Cingolani, Sergei I. Troyanov and Andrei Drozdov

Abstract

From the interaction between [(DPPF[hair space])Pt(az)2] [DPPF = 1,1′-bis(diphenylphosphino)ferrocene; azH = pyrazole (pzH), 3,5-dimethylpyrazole (3,5-Me2pzH) or 4-methylpyrazole (4-MepzH)] and several MX2 acceptors (M = Zn, X = Cl, Br, I or BF4; M = Cd, X = Cl, Br, I or ClO4, M = Hg, X = Cl, Br or I; M = Ba, X = I) 16 novel heteropolymetallic compounds were synthesized and characterized by IR, far-IR, 1H and 31P, and in some cases also with 113Cd, NMR spectroscopy. Heterotrinuclear adducts [(DPPF[hair space])Pt(µ-az)2MX2] were obtained when X = halide, whereas ionic heteropentanuclear complexes [{(DPPF[hair space])Pt(µ2-az)2}2M]2+[X]22– were afforded when X is a weak nucleophile (ClO4 or BF4). Scrambling of the ligands occurred when the reaction between [(DPPF[hair space])Pt(az)2] and Cu(II)X2 salts (X = Cl or Br) was carried out in methanol, [(DPPF[hair space])PtX2] being always obtained. X-Ray crystallography confirms the mononuclear structure of [(DPPF[hair space])Pt(az)2] (azH = pyrazole or 3,5-methylpyrazole), in which the Pt atom is in a distorted cis square planar coordination with the two cyclopentadienyl rings in a staggered conformation. In the heterotrinuclear [(DPPF[hair space])Pt(µ-pz)2CdI2], the cadmium atom is strongly distorted tetrahedral, coordinated by two N-atoms of pyrazolate rings and two iodine atoms.

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