Abstract
The compound [Ren(terpy)(PPh3)2Cl]+ (with counterion Cl- (I) or OTf” (II)) has proven to be a useful synthon
in the synthesis of a series of Re(I) and Re(III) compounds. Compound I can be oxidized in the presence of Cl~
to form [Rera(terpy)(PPh3)Cl2]+ (IV)or Reffl(terpy)Cl3 (V). Compound II can be reduced in the presence of
cyclohexenone to form ReI(terpy)(PPh3)Cl(>/* 12-cyclohexenone) (VI). The chloride on compound VI undergoes
facile substitution to form a series of Re(I)—terpyridyl derivatives (VII— ). The electrochemistry of these
compounds has been studied and compared to that of other known rhenium compounds using an electrochemical
parametrization model. A correlation is drawn between the number and strength of -acidic ligands and the
deviations of the observed II/I reduction potentials from the predicted values. An X-ray crystal structure
determination for II is also reported. [Ren(terpy)(PPh3)2Cl]OTf (II) crystallizes in the triclinic space group PI
(No. 2) with Z= 2 and lattice parameters a= 14.552(7) k,b= 15.726(7) Á,c= 12.215(3) k,a= 109.09(2)°,
ß= 96.98(3)°, and y= 98.42(4)° at -80 °C.
