Complexation of metal carbonyl units with [ alpha -PW sub(11)O sub(39)] super(7-) and [ alpha sub(2)-P sub(2)W sub(17)O sub(61)] super(10- ): insights into the chiral "twisted-sandwich" dimeric structures

Several polyoxometalate-supported metal carbonyl complexes, K sub(7)Na sub(3)P sub(2)W sub(23)O sub(80){Re(CO) sub(3)} sub(2).38H sub(2)O (1), (C sub(3)H sub(10)N) sub(8)Na sub(2)P sub(2)W sub(23)O sub(80){Re(CO) sub(3)} sub(2). 10H sub(2)O (1a) and (C sub(3)H sub(10)N) sub(6)KNa sub(3)P sub(2)W sub(23)O sub(80){Mn(CO) sub(3)] } sub(2).7H sub(2)O (2), have been prepared from the dimerization of the monovacant Keggin [ alpha -PW sub(11)O sub(39)] super(7-) with metal carbonyl complexes [M(CO) sub(3)] super(+) (M = Re, Mn) in acidic aqueous solutions. The resulting "twisted-sandwich" architectures are chiral, but their crystalline solids are racemic. A detailed investigation involving syntheses, crystal structures, and electrochemistry is presented.