ISSN:
0009-2940
Keywords:
Iodine
;
Phosphorus
;
Charge transfer
;
NMR spectroscopy
;
Raman spectroscopy
;
Structure elucidation
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The solid-state and solution structures of Ph3P · I2 have been studied in detail by electronic, 31P{1H}-NMR and Raman spectroscopy as well as conductometric measurements. When 1 : 1 ratios of triphenylphosphane and diiodine are mixed in dichloroethane, the molecular adduct is shown to exist also in solution. On the basis of the overall results, this molecular adduct is best described as a charge-transfer complex of the donor I- with the acceptor Ph3PI+, rather than the charge-transfer complex of the donor Ph3P with the acceptor I2 or the ionic species [Ph3PI]I as previously proposed. When higher diiodine to triphenylphosphane ratios are used, the Ph3P · I2 adduct dissociates to give Ph3PI+ and I3- or I5- depending on the diiodine excess. Previously reported solution data, which were ascribed to the ionic form of the adduct, are instead in agreement with hydrolysis products (Ph3PO, PH3POH+) of the very reactive adduct, formed in the presence of traces of water.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19971300226
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