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DOI: 10.1039/A604305D (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1997, 75-78

Structure–reactivity relationship for the cobalt(III) complex-catalysed hydrolysis of adenosine 3′,5′-cyclic monophosphate[hair space]1

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Makoto Komiyama, Jun Sumaoka, Koji Yonezawa, Yoichi Matsumoto and Morio Yashiro

Abstract

Hydrolysis of adenosine 3′,5′-cyclic monophosphate (cAMP) by cobalt(III) complexes [Co(N4)(H2O)2]3+ (N4: two diamines or one tetraamine) has been systematically studied at pH 7 and 50 oC. Both the catalytic activity and the product distribution are highly dependent on the nature of the amine ligand. The relative catalytic activities are cyclen (4000) > trien (500) > (tme)2 (57) > tren (37) > (tn)2 (22) > 2,3,2-tet (7) > (en)2 (1) ≫ cyclam, cth, dien. The pseudo-first-order rate constant for the cyclen complex (0.05 M) is 1.2 h-1 (half-life 35 min), corresponding to a 1010-fold acceleration with respect to the uncatalysed reaction. Of the two P–O linkages in cAMP, the cyclen, the trien and the 2,3,2-tet complexes preferentially cleave the P–O(5′) linkage, whereas the (tme)2 and the (tn)2 complexes promote P–O(3′) scission. Adenosine is the main product for hydrolysis by the (tme)2 complex, whereas adenosine monophosphates as the hydrolysis intermediates are accumulated in the catalysis by the trien complex.

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