Journal of the Chemical Society. Perkin transactions II p. 829 - 834 (1987)
Update date:2022-08-10
Topics:
Poizat, Olivier
Giannotti, Charles
Sourisseau, Claude
Two reactions are induced from pure solid methyl viologen dichloride, MV2+ (CL-)2, upon heating under vacuum: warming over 50 deg C yields Cl-MV+.Cl. via an intracomplex electron-transfer process; warming to 180 deg C yields 4,4'-bipyridine and CH3Cl, probably via a second intracomplex charge-transfer process.Both these reactions are also shown to occur upon visible excitation of dehydrated MV2+(Cl-)2.In this case, the MV2+ -> MV+. reduction does not arise from direct photochemistry but rather results from thermal activation.Similar treatment of the bromide and iodide salts, MV2+(Br-)2 and MV2+(I-)2, lead only to the dealkylation products.These reactions have been investigated and followed using i.r., Raman, u.v.-visible, and e.s.r. spectroscopy and their mechanisms are discussed.
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