Open AccessInteraction of morpholine and thiomorpholine with molecular diiodine:X‐ray crystal structure of morpholinium triiodide
Author(s) -
Arca Massimiliano,
Cristiani Franco,
Devillanova Francesco A.,
Garau Alessandra,
Isaia Francesco,
Lippolis Vito,
Verani Gaetano,
Demartin Francesco
Publication year - 1997
Publication title -
heteroatom chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.283
H-Index - 42
eISSN - 1098-1071
pISSN - 1042-7163
DOI - 10.1002/(sici)1098-1071(1997)8:2<139::aid-hc6>3.0.co;2-9
Subject(s) - chemistry , adduct , morpholine , raman spectroscopy , triiodide , stoichiometry , crystallography , crystal (programming language) , crystal structure , spectroscopy , yield (engineering) , infrared spectroscopy , organic chemistry , physics , electrode , quantum mechanics , dye sensitized solar cell , computer science , optics , electrolyte , programming language , materials science , metallurgy
The reactions between the donors morpholine (1) and thiomorpholine (2) with I 2 in low polar solvents (C 6 H 6 , CHCl 3 , CH 2 Cl 2 ) and different donor/I 2 concentration ratios (1:1, 1:2, 1:3) yield solids of stoichiometry 1·I 2 , 1H + I − 3 , 1H + I − 5 , 2·I 2 , and 2H + I − 3 . Crystals suitable for X‐ray structure determination have been obtained only for 1 H + I − 3 . All the solids were characterized by FT‐Raman and FT‐IR spectroscopies in the region of the v(I‐I) frequencies. Studies in solution have been carried out on each of the reactions between 1, 2, and N‐methylmorpholine (3) with I 2 . The formation constants of their 1:1 adducts determined at 20°C by UV‐visible spectroscopy are 1781, 8500, and 8400 dm 3 mol −1 , respectively. IR spectroscopy shows that I 2 binds the nitrogen of 1 and 2 both in axial and equatorial positions. Further, FT‐Raman and 13 CNMR spectroscopies support the nature of weak adducts between 1 (2) and the molecular diiodine in solution. © 1997 John Wiley & Sons, Inc.