Coordination Chemistry of Single-Site Catalyst Precursors in Reductively Electropolymerized Vinylbipyridine Films

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• 作者：Daniel P. Harrison ; Alexander M. Lapides ; Robert A. Binstead ; Javier J. Concepcion ; Manuel A. M茅ndez ; Daniel A. Torelli ; Joseph L. Templeton ; Thomas J. Meyer
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：May 6, 2013
• 年：2013
• 卷：52
• 期：9
• 页码：4747-4749
• 全文大小：240K
• 年卷期：v.52,no.9(May 6, 2013)
• ISSN：1520-510X

文摘

Reductive electropolymerization of [Ru^II(PhTpy)(5,5鈥?dvbpy)(Cl)](PF₆) and [Ru^II(PhTpy)(5,5鈥?dvbpy)(MeCN)](PF₆)₂ (PhTpy is 4鈥?phenyl-2,2鈥?6鈥?2鈥?terpyridine; 5,5鈥?dvbpy is 5,5鈥?divinyl-2,2鈥?bipyridine) on glassy carbon electrodes gives well-defined films of poly{[Ru^II(PhTpy)(5,5鈥?dvbpy)(Cl)](PF₆)} (poly-1) or poly{[Ru^II(PhTpy)(5,5鈥?dvbpy)(MeCN)](PF₆)₂} (poly-2). Oxidative cycling of poly-2 with added NO₃^{鈥?/sup> results in the replacement of coordinated MeCN by NO₃鈥?/sup> to give poly{[RuII(PhTpy)(5,5鈥?dvbpy)(NO₃)]+}, and with 0.1 M HClO₄, replacement by H₂O occurs to give poly{[RuII(PhTpy)(5,5鈥?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.}