The syntheses of 2,(3)-(peripheral) and 1,(4)-(non-peripheral) (2-mercaptopyridine)phthalocyanine complexes of titanium(IV) oxide (5a and 6a, respectively), vanadium(IV) oxide (7a and 8a, respectively) and tantalum(V) hydroxide (9a, peripheral only) and their electrochemical characterization are presented in this report. Their electrochemistry is compared to that of thiophenyl and thiobenzyl substituted derivatives. The non-peripherally substituted complexes are more difficult to reduce than peripherally substituted derivatives. In addition, the mercaptopyridine substituted derivatives are more difficult to reduce compared to benzylmercapto and phenylmercapto derivatives, and aryl easier reduce than alkyl substitution. Spectroelectrochemistry of the complexes confirmed metal and ring redox processes for TaPc and TiPc derivatives and ring based processes only for VPc complexes. (C) 2011 Elsevier Ltd. All rights reserved.