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Insertion of Methylthiirane into the P-I Bonds of alpha-P4S3I2

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.

Publication metadata

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


DOI: 10.1002/zaac.200900235


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