Abstract
The preparation of compounds having the general formula R₃MX, where R is an alkyl group, M is P, As or Sb and X is O, S, Se or Te has been carried put previously. The fundamental stretching frequency, ν[subscript S](M=X), has also been determined for P=O, P=S, P=Se, As=O, As=S and As=Se bonds. In the present work the assignment of the M=X stretching frequencies has been extended to include 20 or more compounds, including the alkyl stibine oxides [ν[subscript S](Sb=O) at 450=680 cm⁻¹], alkyl stibine sulfides [ν[subscript S](Sb=S) at 420-450 cm⁻¹], alkyl stibine selenides [ν[subscript S](Sb=Se) at 270-300 cm⁻¹] and alkyl phosphine tellurides [ν[subscript S](P=Te) at 400-520 cm⁻¹]. A correlation has been observed which related the location of these frequencies to the total mass of the molecule and the masses and electronegativities of the respective atoms, M and X. A regression analysis was carried out for the series of R₃MX compounds, while maintaining R constant. The correlation coefficients and the standard deviations for the regression equations were of the same order of magnitude for all the series. For example, in the case of R=butyl, the following relationship was found: ν[subscript S](M=X)(cm⁻¹) = 121.62 + 215.09 (Σm/m[subscript M]m[subscript X])[superscript 1/2]E[subscript M]E[subscript X] with a correlation coefficient of 0.987 and a standard deviation of 43 cm⁻¹. Σm = total mass, m[subscript M] = mass of M, m[subscript X] = mass of X; χ[subscript M] and χ[subscript X], the electronegativities of M and X, respectively. The absolute integrated absorption intensities for five trialkylstibine sulfides were determined. These values were all of the same order of magnitude. For triethylstibine sulfide A = 6.1 x 10³ 1/mol cm². It was also found that the absolute intensities were linearly dependent with Taft's polar and steric parameters.
Chremos, George Nicolaos (1969). The synthesis and infrared spectra of some group VA chalcogenides. Doctoral dissertation, Texas A&M University. Texas A&M University. Libraries. Available electronically from
https : / /hdl .handle .net /1969 .1 /DISSERTATIONS -173870.