Synthesis and Reactions of New Oxorhenium(V) Complexes with Re-Halogen Bonds. X-Ray Crystal Structure of 3-(Benzyl)azapentane-1.5-dithiolato)iodo-Oxorhenium(V).

Treatment of [ReO(SN(R)S)(SMe)] (HSN(R)SH=HS-CH₂ CH₂-N(R)- CH₂ CH₂-SH, R=n-propyl 4a, benzyl 4b) with an excess of CH₃I at room temperature gave the-SCH₃ displaced products [ReO(SN(R)S)I] 5a,b in about 80% yield. [(3-(Benzyl)azapentane-1,5-dithiolato)iodo]oxorheniumV 5b was characterized by single-crystal structure analysis revealing a distorted trigonal bipyramidal geometry with the oxygen and the sulfur atoms forming the equatorial plane. Compounds 5 allow clean transformation to new SNS/thiolato mixed ligand complexes as shown herein by a sample reaction with 1-beta-D-thiogalactose to give 6a.