Spectra and structure of organophosphorus molecules. 39. Microwave, Raman, and infrared spectra of trimethylphosphine sulfide and three deuteriated species

Journal Article · Wed Jan 25 04:00:00 EST 1989 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00301a029· OSTI ID:5144434

Durig, J R; Chatterjee, K K ^[1]

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1. Univ. of South Carolina, Columbia (USA)

Microwave spectra from 26.5 to 39.0 GHz of (CH{sub 3}){sub 3}PS, (CH{sub 3}){sub 2}(CD{sub 3})PS, (CH{sub 3})(CD{sub 3}){sub 2}PS, (CD{sub 3}){sub 3}PS, and (CH{sub 3}){sub 3}P{sup 34}S have been measured at ambient temperature, and the observed transitions have been assigned for the ground vibrational states for each molecule. From a diagnostic least-squares adjustment to fit nine independent rotational constants, the following r{sup 0} structural parameters were obtained: r(P{l reversible}S) = 1.936 {plus minus} 0.003 {angstrom}, r(P-C) = 1.814 {plus minus} 0.001 {angstrom}, r(C-H) = 1.094 {plus minus} 0.003 {angstrom}, {angle}CPS = 114.36 {plus minus} 0.09{degree}, {angle}HCH = 109.52 {plus minus} 0.04{degree}, and methyl tilt angle of 3.7 {plus minus} 1.3{degree}. The bond length for the P{l reversible}S bond lies close to the value expected for a double bond, and it is in agreement with the previously reported value for this bond from an electron diffraction study. The low-temperature mid-infrared spectra (3200-500 cm{sup {minus}1}) and the Raman spectra (3200-50 cm{sup {minus}1}) at ambient temperature have also been recorded for the solid states of all five isotopic species. The far-infrared spectra of the d{sub 0} and d{sub 9} species have also been measured as Nujol mulls. Assignments of the fundamental vibrations have been made by assuming an effective C{sub 3v} symmetry for (CH{sub 3}){sub 3}PS and (CD{sub 3}){sub 3}PS and C{sub s} symmetry for (CH{sub 3}){sub 2}(CD{sub 3})PS and (CH{sub 3})(CD{sub 3}){sub 2}PS. The proposed assignment of the normal modes is supported by a normal-coordinate calculation utilizing a simple valence force field to calculate the fundamental frequencies and the potential energy distribution. These results are compared to corresponding quantities for some similar molecules. 8 tabs., 5 figs., 19 refs.

• OSTI ID: 5144434
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 28:2; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ALKANES
DATA
DEUTERIUM
EXPERIMENTAL DATA
HYDROCARBONS
HYDROGEN ISOTOPES
INFORMATION
INFRARED SPECTRA
ISOTOPE APPLICATIONS
ISOTOPES
LABELLED COMPOUNDS
LIGHT NUCLEI
MICROWAVE SPECTRA
MOLECULAR STRUCTURE
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANIC SULFUR COMPOUNDS
RAMAN SPECTRA
SPECTRA
STABLE ISOTOPES
TRACER TECHNIQUES