Kinetic H/D exchange study of Co(III) coordination compounds of diazines using NMR spectroscopy

Abstract

The Co(III) diazines complexes having composition (NH3) 5CoPhtz)(ClO4), (1) (Phtz = phthalazine), (NH 3)5CoPydz)(ClO4)3 (2) (Pydz = pyradazine), (NH3)5Co(3-Me-Pydz)(ClO4) 3 (3) (3-Me-Pydz = 3-methyl pyradazine) and (NH3) 5Co(3-MePhtz)(ClO4)3 (4) (3-MePhtz = 3-methyl phthalazine), (NH3)5Co(ImH)(ClO4), (5) (ImH = imidazole), (NH3)5Co(NMeIm)(ClO4) 3 (6) (N-MeIm = N-methylimidazole) undergo OD--catalyzed H/D exchange at the ortho position of the coordinated site. Rate constants for H/D exchange of these complexes at 25°C or 60°C were obtained in alkaline D2O solution using NMR spectroscopy. Reaction rate for (NH3)5CoPhtz)(ClO4)3, (NH 3)5CoPydz)(ClO4)3, (NH 3)5Co(3-MePydz)(ClO4)3 and (NH3)5Co(3-MePhtz)(ClO4)3 at 25°C are faster compared to (NH3)5Co(ImH)(ClO 4)3, (NH3)5Co(N-MeIm)(ClO 4)3 (7). However (NH3) 5CoImCo(NH3)5Br5 complex does not H/D exchange at 60°C even in strong alkaline D2O solution

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