Unusual Stability and Carbon Acidity of a Dicationic Carbon Species

Abstract

1,1'-Methylenebis(pyridinium) dication (MDP) is an unusual ion with two formal positively charged substituents attached to a central carbon, yet it is remarkably stable to hydrolysis at pH < 8. However, above this pH it undergoes a biphasic reaction liberating two equiv of pyridine sequentially. The rate of the first phase is second order in hydroxide ion, while that of the second is pH-independent. The first phase is also accompanied by the generation of a chromophore at 366 nm, which has been identified as a pyridine-ring-opened unsaturated iminoaldehyde formed by an ANRORC-type mechanism. This intermediate then undergoes ring closure to give the second equiv of pyridine and formaldehyde. Below pD 8 there is a very slow alternative pathway for degradation that is first order in hydroxide ion, liberates only one equiv of pyridine, and forms N-(hydroxymethyl)pyridinium ion. Deuterium exchange of the central methylene in D2O is faster than the breakdown of MDP and is predominantly OD(-)-catalyzed with a small amount of buffer catalysis. The estimated pKa of MDP dication in H2O, 21.2 at 25 °C and I = 1.0 M (KCl), is unexpectedly high but is about 9 units lower than that for the monocationic N-methylpyridinium ion. Deuterium exchange also occurs at the 2 and 6 positions of the pyridinium rings, but at a lower rate that is first order in deuteroxide ion and competitive with the breakdown of MDP only below pD 11.