Reactions of electrophiles with [ButN)2ReVI(µ-NBut)]2

Abstract

The interaction of [(Bu^tN)₂Re^VI(µ-NBu^t)]₂1 with trifluoromethanesulfonic acid gave the amido complex [(Bu^tN)(Bu^tHN)Re(µ-NBu^t)₂Re(NBu^t)₂][CF₃SO₃], where the cation has a structure very similar to that of its manganese(VI) analogue. The interaction of 1 with silver triflate differs from the similar reaction with [(Bu^tN)₂Mn^VI(µ-NBu^t)]₂ in that a silver complex {[(Bu^tN)Re(µ-NBu^t)]₂(µ-NBu^t)₂Ag(µ-O₃SCF₃)}₂ that has NBu^t groups bridging both rhenium and silver atoms with the latter having µ-O₃SCF₃ bridges is formed. A similar complex [(Bu^tN)Re(µ-NBu^t)]₂(µ-NBu^t)₂Cu₂(O₃SCF₃)₂ was obtained by interaction of 1 with Cu(O₃SCF₃)·0.5C₆H₆ but this has Re(µ-NBu^t)Cu(O₃SCF₃) groups. Interaction of 1 with Al(O₃SCF₃)₃·nCF₃SO₃H in CH₂Cl₂ gave a linear molecule (Bu^tN)₂Re(µ-NBu^t)₂Re(NBu^t)(µ-OH)₂Al(O₃SCF₃)₃(H₂O). The crystal structures of four compounds have been determined. An improved synthesis of 1 involving Na/Hg reduction of Re(NBu^t)₃I was elaborated.