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Lookup NU author(s): Dr Bruce Tattershall
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Rac-methylthiirane inserted into the P-I bonds of alpha-P4S3I2, giving two diastereomers of exo,exo-alpha-P4S3(SCHMeCH2I)I and three diastereomers of exo,exo-alpha-P4S3(SCHMeCH2I)(2), as kinetic products, identified by P-31 and C-13 NMR spectroscopy in the reaction solutions. Ab initio modelling, using the DF MPW1PW91 method, showed that corresponding products containing the SCH2CHIMe substituent should be more stable, but only alpha-P4S3(SCHMeCH2I)(SCH2CHIMe) was suggested by the NMR evidence as a lower yield product. The initially formed thiolates were sulfurised by further methylthiirane on heating or in the presence of the sulfur transfer catalyst Re(O)Cl-3(PPh3)(2), to give low concentrations of alpha-P4S3(S)(SCHMeCH2I)I and alpha-P4S3(S)(SCHMeCH2I)(2), in which a monocoordinate sulfur atom was attached to a phosphorus atom carrying the thiolate group. The number of diastereomers appropriate for only one orientation of the terminal Sulfur relative to the cage skeleton was found in significant concentration in each case, in contrast to previous work on sulfurisation of alpha-P4S3 diamides.
Author(s): Tattershall BW, Geneux NS, Holmes KE, Hargreaves MD, McMorrow G
Publication type: Article
Publication status: Published
Journal: Zeitschrift fuer Anorganische und Allgemeine Chemie
Year: 2009
Volume: 635
Issue: 13-14
Pages: 2222-2229
ISSN (print): 0044-2313
ISSN (electronic): 1521-3749
Publisher: Wiley - VCH Verlag GmbH & Co. KGaA
URL: http://dx.doi.org/10.1002/zaac.200900235
DOI: 10.1002/zaac.200900235
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