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Tin(IV) and organotin(IV) derivatives of novel β-diketones: Part IV. Triorganotin(IV) complexes of fluorinated 4-acyl-5-pyrazolones. Crystal structure of (1-(4-trifluoromethylphenyl)-3-methyl-4-acetylpyrazolon-5-ato)triphenyltin(IV)
Authors:FabioMarchetti  Claudio Pettinari  Augusto Cingolani  Lauro Brocanelli  Miriam Rossi  Francesco Caruso  
Institution:a Dipartimento di Scienze Chimiche, Università degli Studi, via S. Agostino 1, I-62032 Camerino, Macerata, Italy;b Vassar College, Department of Chemistry, Poughkeepsie, NY 12604, USA;c Istituto di Strutturistica Chimica G. Giacomello, CNR, CP 10, I-00016 Monterotondo Stazione, Roma, Italy
Abstract:The synthesis of three 1-(4-trifluoromethylphenyl)-3-methyl-4-R1(C=O)-5-pyrazolone proligands LH (L1H; R1=C6H5: L2H; R1=CH3: L3H; R1=CF3) and their interaction with R3Sn(IV) acceptors (R=Me, Bun, Ph) are reported. When R=Me or Bun, aquo (4-acylpyrazolonate)SnR3(H2O) derivatives are obtained and the anionic donors 4-acylpyrazolonate (L) act in the O–monodentate form. These triorganotin complexes are not stable in chlorohydrocarbon solvents and decompose to R4Sn and bis(4-acyl-5-pyrazolonate)2SnR2. When R=Ph, stable (4-acyl-5-pyrazolonate)SnPh3 derivatives, both in solution and in the solid state, are obtained. The crystal structure of (1-(4-trifluoromethylphenyl)-3-methyl-4-acetylpyrazolon-5-ato)triphenyltin(IV) shows a five-coordinate tin atom in a strongly distorted cis-bipyramidal trigonal environment (axial angle=161.2(2)°) with the acylpyrazolonate donor acting as an asymmetric O2–bidentate species (Sn–O(1)=2.081(6) Å: Sn–O(2)=2.424(5) Å). Electronic effects are responsible for the different behavior shown by these trialkyl and triphenyl derivatives.
Keywords:4-Acyl-5-pyrazolones  Crystal structure  IR  NMR  Triorganotin(IV) complex
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