55344-99-5Relevant academic research and scientific papers
Crystal structure of triphenylphosphine sulfide diiodine; the first crystallographically characterised 1:1 molecular charge-transfer complex of a tertiary phosphine sulfide with diiodine
Apperley, David C.,Bricklebank, Neil,Burns, Sally L.,Hibbs, David E.,Hursthouse, Michael B.,Malik, K. M. Abdul
, p. 1289 - 1292 (2007/10/03)
In CH2Cl2 solution, Ph3PS and diiodine react to form a molecular 1:1 charge-transfer complex. The complex has been studied in solution using 31P-{H} NMR and UV/VIS spectroscopy. Single-crystal X-ray diffraction and solid-state 31P-{H} NMR studies of Ph3PS·I2 show that the molecular structure is maintained in the solid phase. The structure of Ph3PS·I2 is novel and contradicts previous results which indicated that a 1:1 (Ph3PS: I2) complex could not be isolated in the solid state. The I-I distance [2.823(1) A] and the S-I distance [2.753(2) A] in Ph3PS·I2 are comparable with those in charge-transfer complexes of related sulfur donors. However, the I-I distance in Ph3PS·I2 is shorter than that in Ph3PSe·I2 reflecting the weaker donor power of the Ph3PS towards diiodine. The NMR spectroscopic results on Ph3PS·I2 and the analogous Ph3PO and Ph3PSe compounds indicate that the stability of the Ph3PE·I2 complexes increases in the order E = Se > S ? O.
1-Iodoacetylenes. Part 2. Formation Constants of their Complexes with Lewis Bases
Laurence, Christian,Queignec-Cabanetos, Michele,Wojtkowiak, Bruno
, p. 1605 - 1610 (2007/10/02)
Formation constants of the complexes of 1-iodoacetylenes (1)-(8) with Lewis bases (9)-(15) have been measured in solution by i.r. spectrophotometry.The stoichiometry of the complexes, the influence of the solvent on the equilibrium position, the existence of linear free energy relationships in the series of iodinated Lewis acids RI, where R=I, Br, Cl, CN, and CCX, and the relation between i.r. frequency shifts and stability constants are discussed.With any electron donor, 1-iodoacetylenes form less stable complexes than those formed by iodine cyanide.With hard bases, iodocyanoacetylene (8) and ethyliodopropiolate (7) give complexes wich are, respectively, more stable than and as stable as those with iodine; however, iodine complexes with soft bases are more stable.This is rationalized, in terms of empirical acidity scales, by the necessity to correlate the thermodynamic and spectroscopic properties of the RI complexes by a double scale equation.
