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A comprehensive study of (CH 3 ) 2 CHOC(S)SC(O)OCH 3 using matrix isolation technique, X‐ray analysis, spectroscopic studies and theoretical calculations
Author(s) -
Tobón Yeny A.,
Romano Rosana M.,
HeyHawkins Evamarie,
Boese Roland,
Védova Carlos O. Della
Publication year - 2009
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1525
Subject(s) - chemistry , conformational isomerism , matrix isolation , infrared spectroscopy , raman spectroscopy , spectroscopy , methyl formate , yield (engineering) , crystallography , analytical chemistry (journal) , molecule , organic chemistry , materials science , metallurgy , physics , quantum mechanics , methanol , optics
Abstract Potassium isopropyl xanthate, (CH 3 ) 2 CHOC(S)SK, reacts with methyl chloroformiate ClC(O)OCH 3 to yield (methoxycarbonyl) (2‐propoxythiocarbonyl) sulfide, (CH 3 ) 2 CHOC(S)SC(O)OCH 3 . This novel xanthogen formate was characterized by 1 H and 13 C{ 1 H} NMR spectroscopy, mass spectrometry and IR and Raman spectroscopy. The structure of a single crystal of (CH 3 ) 2 CHOC(S)SC(O)OCH 3 was determined by X‐ray diffraction analysis at 173 K. The conformational properties have been studied by liquid IR and Raman spectroscopy, matrix isolation spectroscopy together with photochemical studies and quantum chemical calculations (HF and B3LYP methods with the 6‐31+G* basis set). The analysis of the IR spectrum of liquid (CH 3 ) 2 CHOC(S)SC(O)OCH 3 suggests the presence of two conformers in equilibrium at room temperature. However, in the photochemical matrix study, an equilibrium of three conformers was detected. These forms were further characterized by theoretical calculations. Different photolysis products, such as CH 3 OC(O)SCH(CH 3 ) 2 , OCS, CO, CO 2 and CS 2 , were identified by matrix spectroscopy. The IR absorptions of CH 3 OC(O)SCH(CH 3 ) 2 , for which literature data are scarce, were analysed in the light of the results of appropriate theoretical calculations. Copyright © 2009 John Wiley & Sons, Ltd.