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Lookup NU author(s): Dr Bruce Tattershall, Gina Valks
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Reaction of a mixture of bicyclic phosphorus sulfide selenide iodides alpha-P4SnSe3-nI2 (n = 0-3) with (PtNH2)-N-i and Et3N gave corresponding diamides alpha-P4SnSe3-n(NHPri)(2) (n = 0-3) and imides alpha-P4SnSe3-n(mu-NPri) (n = 2-3), identified in solution by P-31 NMR. In one isomer of alpha-P4S2Se(mu-NPri), the C-2 symmetry of imides such as alpha-P4S3(mu-NPri) was broken, allowing relative assignment of (2)J NMR couplings to the PNP bridge and the PSP bridge opposite to it. The coupling through the sulfur bridge was found to be reduced to ca. zero, in contrast to previous assumptions for this class of compounds. Ab initio models were calculated at the MPW1PW91/svp level for the sulfide selenide imides and for a selection of bond rotamers of the diamides, and at the MPW1PW91/LanL2DZ(d) level for the sulfide selenide diiodides. Different skeletal isomers were prevalent for the mixed chalcogenide diamides than for the diiodides, showing that exchange of chalcogen between skeletal positions took place in the amination reaction even at room temperature. Similar differences to those observed were predicted by the models, suggesting that equilibrium was attained.
Author(s): Tattershall BW, Holmes KE, Tweedy C, Valks GC
Publication type: Article
Publication status: Published
Journal: Zeitschrift für anorganische und allgemeine Chemie
Year: 2008
Volume: 634
Issue: 10
Pages: 1703-1710
ISSN (print): 0044-2313
ISSN (electronic): 1521-3749
Publisher: Wiley
URL: http://dx.doi.org/10.1002/zaac.200800117
DOI: 10.1002/zaac.200800117
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