No abstract

Rac‐methylthiirane inserted into the P–I bonds of α‐P4S3I2, giving two diastereomers of exo,exo‐α‐P4S3(SCHMeCH2I)I and three diastereomers of exo,exo‐α‐P4S3(SCHMeCH2I)2, as kinetic products, identified by 31P and 13C 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 α‐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)Cl3(PPh3)2, to give low concentrations of α‐P4S3(S)(SCHMeCH2I)I and α‐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 ofα‐P4S3 diamides. Supporting information for this article is available on the WWW under http://www.wiley‐vch.de/contents/jc_2260/2009/index.htm or from the author.