title: Coordination chemistry of single-site catalyst precursors in reductively electropolymerized vinylbipyridine films.
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.
authors.affiliation: Department of Chemistry, Virginia Military Institute, Lexington, Virginia 24450, United States.
authors.forename: Daniel P
authors.initials: DP
authors.lastname: Harrison
authors.forename: Alexander M
authors.initials: AM
authors.lastname: Lapides
authors.forename: Robert A
authors.initials: RA
authors.lastname: Binstead
authors.forename: Javier J
authors.initials: JJ
authors.lastname: Concepcion
authors.forename: Manuel A
authors.initials: MA
authors.lastname: Méndez
authors.forename: Daniel A
authors.initials: DA
authors.lastname: Torelli
authors.forename: Joseph L
authors.initials: JL
authors.lastname: Templeton
authors.forename: Thomas J
authors.initials: TJ
authors.lastname: Meyer