An anionic {[MnCo(ox)(3)](-)}(n) network with appropriate cavities for theenantioselective recognition and resolution of the hexacoordinated monocation [Ru(bpy)(2)(ppy)](+) (bpy = bipyridine, ppy = phenylpyridine)
M. Brissard et al., An anionic {[MnCo(ox)(3)](-)}(n) network with appropriate cavities for theenantioselective recognition and resolution of the hexacoordinated monocation [Ru(bpy)(2)(ppy)](+) (bpy = bipyridine, ppy = phenylpyridine), EUR J INORG, (7), 2001, pp. 1745-1751
Partial resolution of the rac-[Ru(bpy)(2)(ppy)](+) monocation into [Delta -
Ru(bpy)(2)(ppy)]PF6 (1 Delta) (ee = 44%) and [Lambda -Ru(bpy)(2)(pPY)]PF6 (
I Lambda) (ee = 50%) enantiomers was achieved by an unprecedented resolving
process which involves the diastereoselective preparation of optically act
ive networks of the type ([Lambda -Ru(bpy)(2)(ppy)][Mn-Lambda -Co(ox)(3)])(
n) (2 Lambda) and ([Delta -Ru(bpy)(2)(ppy)][Mn-Delta -Co(ox)(3)])(n) (2 Del
ta). In these optically active inorganic polymers, the counter-monocation [
Ru(bpy)(2)(ppy)](+) of appropriate configuration occupies the cavities whil
e the excess [Ru(bpy)(2)(ppy)](+), of opposite configuration, remains in so
lution and is thus recovered. Anion metathesis of the optically active [Ru(
bpy)(2)(ppy)]PFB (1 Delta) (ee = 44%) and (1 Lambda) (ee = 50%) with [1-cin
chonidinium][Delta -trisphat] [trisphat = tris (tetrachlorobenzenediolato)-
phosphate (V)] provides the related diastereomers [Delta -Ru(bpu)(2)(ppy)][
Delta -trisphat] (3 Delta) (de= 44%) and [Lambda -Ru(bpy)(2)(ppu) ][Delta -
trisphat] (3 Lambda) (de = 50%) in 60% yield. Their diastereomeric excesses
were assessed by H-1 NMR analysis. All products were fully characterized a
nd the absolute configuration was determined by circular dichroism techniqu
es in solution or in the solid state. Additionally the X-say structure of [
Ru(bpy)(2)(PPY)]PF6 (1) Was determined.