Substituent and isomer effects on the structura
l, spectroscopic, (UV-visib
le and ESR) and e
lectrochemica
l propertiesof dirhodium(III,II) comp
lexes containing four identica
l unsymmetrica
l bridging
ligands are reported for seven re
latedcompounds of the type Rh
2(L)
4C
l where L = 2-(2-f
luoroani
lino)pyridinate (2-Fap), 2-(2,6-dif
luoroani
lino)pyridinate(2,6-F
2ap), 2-(2,4,6-trif
luoroani
lino)pyridinate (2,4,6-F
3ap), or 2-(2,3,4,5,6-pentaf
luoroani
lino)pyridinate (F
5ap) anion.Rh
2(2-Fap)
4C
l exists on
ly in a (4,0) isomeric conformation whi
le Rh
2(2,6-F
2ap)
4C
l, Rh
2(2,4,6-F
3ap)
4C
l, and Rh
2(F
5ap)
4C
l exist as both (4,0) and (3,1) isomers. It had ear
lier been demonstrated that Rh
2(L)
4C
l comp
lexes canadopt different geometric conformations of the bridging
ligands, but the current study provides the first examp
lewhere two geometric isomers of Rh
25+ comp
lexes are obtained for one compound using the same synthetic procedure.The synthesis, structura
l, spectroscopic, and/or e
lectrochemica
l properties of (3,1) Rh
2(2,6-F
2ap)
4CN and (4,0)Rh
2(2,4,6-F
3ap)
4(C
C)
2Si(CH
3)
3 are a
lso reported and the data on these compounds is discussed in
light of theirparent comp
lexes, (3,1) Rh
2(2,6-F
2ap)
4C
l and (4,0) Rh
2(2,4,6-F
3ap)
4C
l.