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

Bruce William Tattershall (1) , Nicholas Geneux (1) , Kathryn Holmes (1) , Michael Hargreaves (1) , Glenn Mcmorrow (1)

1 School of Chemistry [Newcastle]

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 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 1-coordinate 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 α-P₄S₃ diamides.

Mots clés: Physical Sciences

Bruce William Tattershall, Nicholas Geneux, Kathryn Holmes, Michael Hargreaves, Glenn Mcmorrow. Insertion of Methylthiirane into the P-I Bonds of α-P₄S₃I₂. Journal of Inorganic and General Chemistry / Zeitschrift für anorganische und allgemeine Chemie, 2009, 635 (13-14), pp.2222. ⟨10.1002/zaac.200900235⟩. ⟨hal-00518303⟩