108696-03-3Relevant articles and documents
Stoichiometry of diorganotin dihalide adducts in solution
Yoder, Claude H.,Mokrynka, Dian,Coley, Suzanne M.,Otter, Julie C.,Haines, Ronald E.,Grushow, Alex,Ansel, Lori J.,Hovick, James W.,Mikus, Joseph,Shermak, Michele A.,Spencer
, p. 1679 - 1684 (2008/10/08)
The formation of Lewis acid-base adducts of diorganotin dihalides of the type R2SnX2, where R = CH3, C2H5, C3H7, n-C4H9, i-C4H9, or C6H5 and X = Cl or Br, with a variety of bases (triphenylphosphine oxide [TPPO], Me2SO, DMA, diphenyl sulfoxide, dibenzyl sulfoxide, pyridine N-oxide, and acetonitrile) was studied by both NMR spectroscopy and calorimetry. The 31P chemical shift of TPPO and the 119Sn shift of the acid were monitored as a function of concentration. The effects of different equilibria including formation of the 1:1 adduct, the 1:2 adduct, simultaneous formation of the 1:1 and 1:2 adducts, and simultaneous formation of the 1:1 adduct and either associated acid, associated base, or associated adduct on the NMR shifts as a function of concentration were determined by computer simulation. The experimentally observed plots can be attributed to predominant formation of the 1:1 adduct along with the associated adduct. The formation of the 1:2 adduct also occurs in solution as demonstrated by isolation of 1:2 adducts and the curvature obtained in the chemical shift plots for weak acids and bases. Calorimetric data were analyzed by schematic mapping and show that the only model that successfully reproduces the data is predominant formaton of the 1:1 adduct. The size of the substituents on the acid was found to have a significant effect on the equilibrium constants; the constants for di-tert-butyltin dichloride were a factor of 100 lower than those of dimethyltin dichloride. Base strengths toward dimethyltin dichloride vary in the order TPPO > pyridine N-oxide > Me2SO ≥ DMA ≥ dibenzyl sulfoxide ≥ diphenyl sulfoxide > acetonitrile. Previous reports that the 1:2 adducts are favored for the dihalotins are most likely a result of the use of excess base to precipitate the 1:2 adduct and the generally greater insolubility of the 1:2 adduct.