Functionalized bis(pyrazol-1-yl)methanes by organotin halide on the methine carbon atom and their related reactions

The modification of bis(pyrazol-1-yl)methanes by organotin halide on the methine carbon atom has been successfully carried out, and their related reactions have also been studied. Bis(3,5-dimethylpyrazol-1-yl)(iododiphenylstannyl)methane [Ph2ISnCH(3,5-Me2Pz)2] can be obtained by the selective cleavage of the Sn–Csp2Sn–Csp2 bond in bis(3,5-dimethylpyrazol-1-yl)triphenylstannylmethane with I2 in a 1:1 molar ratio, while {di(tert -butyl)chlorostannyl}bis(3,5-dimethylpyrazol-1-yl)methane [(t -Bu)2ClSnCH(3,5-Me2Pz)2] and {di(tert -butyl)chlorostannyl}bis(3,4,5-trimethylpyrazol-1-yl)methane [(t -Bu)2ClSnCH(3,4,5-Me3Pz)2] are easily prepared by the reaction of the bis(3,5-dimethylpyrazol-1-yl)methide or bis(3,4,5-trimethylpyrazol-1-yl)methide anion with di(tert -butyl)tin dichloride. The molecular structure of [(t -Bu)2ClSnCH(3,5-Me2Pz)2] determined by X-ray structure analysis indicates that bis(3,5-dimethylpyrazol-1-yl)methide acts as a bidentate monoanionic κ2-[C,N] chelating ligand. Reaction of these bis(pyrazol-1-yl)methanes functionalized by organotin halide with W(CO)5THF results in the oxidative addition of the relative electrophilic Sn–X (X = Cl or I) bond instead of the Sn–Csp3Sn–Csp3 bond to the tungsten(0) atom, yielding new metal–metal bonded complexes R2SnCHPz2W(CO)3X (R = Ph or t-Bu, Pz represents substituted pyrazol-1-yl). Furthermore, treatment of the oxidative addition product (t-Bu)2SnCH(3,5-Me2Pz)2W(CO)3Cl with n-BuLi results in known complex CH2(3,5-Me2Pz)2W(CO)4 with the loss of the organotin fragment. In addition, reaction of Ph2ISnCH(3,5-Me2Pz)2 with 2-PySNa (Py = pyridyl) leads to the replacement of iodide by 2-PyS− anion to give Ph2(2-PyS)SnCH(3,5-Me2Pz)2, which subsequently reacts with W(CO)5THF to result in the decomposition of this ligand, also yielding the known bis(3,5-dimethylpyrazol-1-yl)methane derivative of CH2(3,5-Me2Pz)2W(CO)4.