Coordination chemistry of single-site catalyst precursors in reductively electropolymerized vinylbipyridine films

Daniel P Harrison; Alexander M Lapides; Robert A Binstead; Javier J Concepcion; Manuel A Méndez; Daniel A Torelli; Joseph L Templeton; Thomas J Meyer

doi:10.1021/ic302472r

Coordination chemistry of single-site catalyst precursors in reductively electropolymerized vinylbipyridine films

Inorg Chem. 2013 May 6;52(9):4747-9. doi: 10.1021/ic302472r. Epub 2013 Apr 24.

Authors

Daniel P Harrison¹, Alexander M Lapides, Robert A Binstead, Javier J Concepcion, Manuel A Méndez, Daniel A Torelli, Joseph L Templeton, Thomas J Meyer

Affiliation

¹ Department of Chemistry, Virginia Military Institute, Lexington, Virginia 24450, United States.

PMID: 23614858
DOI: 10.1021/ic302472r

Abstract

Reductive electropolymerization of [Ru(II)(PhTpy)(5,5'-dvbpy)(Cl)](PF6) and [Ru(II)(PhTpy)(5,5'-dvbpy)(MeCN)](PF6)2 (PhTpy is 4'-phenyl-2,2':6',2″-terpyridine; 5,5'-dvbpy is 5,5'-divinyl-2,2'-bipyridine) on glassy carbon electrodes gives well-defined films of poly{[Ru(II)(PhTpy)(5,5'-dvbpy)(Cl)](PF6)} (poly-1) or poly{[Ru(II)(PhTpy)(5,5'-dvbpy)(MeCN)](PF6)2} (poly-2). Oxidative cycling of poly-2 with added NO3(-) results in the replacement of coordinated MeCN by NO3(-) to give poly{[Ru(II)(PhTpy)(5,5'-dvbpy)(NO3)](+)}, and with 0.1 M HClO4, replacement by H2O occurs to give poly{[Ru(II)(PhTpy)(5,5'-dvbpy)(OH2)](2+)} (poly-OH2). Although analogous aqua complexes (e.g., [Ru(tpy)(bpy)(OH2)](2+)) undergo rapid loss of H2O to MeCN in solution, poly-OH2 and poly-OH2(+) are substitutionally inert in MeCN. The substitution chemistry is reversible, with reductive scans of poly-1 or poly-OH2 in MeCN resulting in poly-2, although with some loss of Faradaic response.