Infrared Spectra of Triphenyltin lsoselenocyanate and Its Adducts with O- and N-Donor Ligands
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Department of Chemistry, McGill University, Montreal, Quebec, Canada, H3A 2K6
The preparation and properties of triphenyltin isoselenocyanate have been reinvestigated. Infrared spectra show that the solid is polymeric with strong Sn—N and weak Sn— Se bonds ; in benzene or CH2CI2 solutions, CN values are consistent with the presence of both Ph3SnNCSe and Ph3SnSeCN. In a variety of donor solvents (tetrahydrofuran, acetone, acetonitrile, pyridine (py), and N,N'-dimethylformamide (DMF)), increasing donor power causes adduct formation and then ionisation. Infrared data indicate that 1 :1 adducts of triphenyltin isoselenocyanate with hexamethylphosphorariide (HMPA), triphenylphosphine oxide (TPPO), 2,4,6-collidine-N-oxide (collO), dimethyl sulphoxide (DMSO), pyridine-N-oxide (pyO), 4-picoline-N-oxide (4-picO), β-Picoline (β-pic), and \(\gamma\)-picoline (\(\gamma\)-pic), as well as Ph3SnNCSe.L (L=py or DMF), are isoselenocyanates. For equilibria in CH2CI2 solution at 22°, K=1.2±0.3 for Ph3SnNCSe\(\rightleftharpoons\)Ph3SoSeCN, while dissociation constants are estimated to be 3 x 10-3, 1.6 x 10-3, 8 x 10-4 and 1.7 x 10-3 M for Ph3SnNCSe.L\(\rightleftharpoons\)Ph3SnNCSe+L, where L=DMF, py, \(\gamma\)-plc, and β-pic, respectively.
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