Role of intramolecular hydrogen bonding in the redox chemistry of hydroxybenzoate-bridged paddlewheel diruthenium(ii,ii) complexes

Wataru Kosaka, Yudai Watanabe, Kinanti Hantiyana Aliyah, Hitoshi Miyasaka

Research output: Contribution to journalArticlepeer-review

Abstract

The synthesis of a series oftrans-heteroleptic paddlewheel diruthenium(ii,ii) complexes with various hydroxy-substituted benzoate ligands, [Ru2((OH)xPhCO2)2(2,6-(CF3)2PhCO2)2(THF)2] ([RuII,II2]) as tetrahydrofuran (THF) adducts is reported, where (OH)xPhCO2stands foro-hydroxybenzoate (o-OH),m-hydroxybenzoate (m-OH),p-hydroxybenzoate (p-OH), 2,3-dihydroxybenzoate (2,3-(OH)2), 2,4-dihydroxybenzoate (2,4-(OH)2), 2,5-dihydroxybenzoate (2,5-(OH)2), 2,6-dihydroxybenzoate (2,6-(OH)2), or 3,4-dihydroxybenzoate (3,4-(OH)2), and 2,6-(CF3)2PhCO2represents 2,6-bis(trifluoromethyl)benzoate. In this heteroleptic series, the redox potential (E1/2) of the [Ru II,II2]/[Ru II,III2]+couple in THF varies over a wide range, from −18 mV (vs.Ag/Ag+) forp-OHto 432 mV for2,6-(OH)2. The redox properties are linearly dependent on the acidity (pKa) of the OH-substituted benzoic acids, but do not depend on the number ofortho-substituted hydroxy (o-OH) groups. This indicates that the steric effect ofo-substituents is irrelevant in the case of hydroxyl groups, owing to the formation of intramolecular hydrogen bonds between theo-OH group and carboxylate oxygens. The value of the Hammett constantσofor theo-OH substituent was determined to be 0.667, indicating a strongly electron-withdrawing character, contrary to the expectation of electron-donating character for an OH group. The redox properties of the compounds were well explained in a framework of Hammett analyses and were also consistent with their HOMO energy levels evaluated by DFT calculations based on the atomic coordinates. The unexpected electron-withdrawing character of theo-OH groups could be attributed to the direct effect of intramolecular hydrogen bonding on the charge density on the carboxylate oxygen.

Original languageEnglish
Pages (from-to)85-94
Number of pages10
JournalDalton Transactions
Volume51
Issue number1
DOIs
Publication statusPublished - 2022 Jan 7

ASJC Scopus subject areas

  • Inorganic Chemistry

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