Ruthenium ammine/crown ether interactions in solution: Effects of modification of both guest and host on the strength of second-sphere complexation

Matthew D. Todd, Yuhua Dong, Jennifer Horney, Dong I. Yoon, Joseph T Hupp

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

Charge-transfer absorption, electrochemical, and NMR-NOE studies of monomeric and dimeric (ligand-bridged) ruthenium ammine guest interactions with several crown ether hosts show that second-sphere complexation is prevalent in nitromethane as solvent and that complexation or binding constants can be varied by ca. 108-fold by modifying both guest and host properties. For hosts, larger binding constants are obtained with larger macrocycles and with more flexible macrocycles (i.e. dicyclohexano vs dibenzo crowns). For guests, larger binding constants are observed in higher oxidation states and in the presence of strongly electron-withdrawing ancillary ligands. In all cases, binding appears to be driven primarily by ammine hydrogen/ether oxygen (Lewis acid/base) interactions. Evidence is also found, however, for contributions from favorable benzene(crown)/pyridine(complex) interactions and (apparently) benzene(crown) → Ru(III) charge-transfer (donor/acceptor) interactions.

Original languageEnglish
Pages (from-to)2001-2004
Number of pages4
JournalInorganic Chemistry
Volume32
Issue number10
Publication statusPublished - 1993

Fingerprint

ammines
Crown Ethers
Ruthenium
Benzene
Complexation
ruthenium
Charge transfer
ethers
Ligands
Lewis Acids
Ether
Hydrogen
benzene
charge transfer
Nuclear magnetic resonance
interactions
Oxygen
Oxidation
nitromethane
ligands

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Ruthenium ammine/crown ether interactions in solution : Effects of modification of both guest and host on the strength of second-sphere complexation. / Todd, Matthew D.; Dong, Yuhua; Horney, Jennifer; Yoon, Dong I.; Hupp, Joseph T.

In: Inorganic Chemistry, Vol. 32, No. 10, 1993, p. 2001-2004.

Research output: Contribution to journalArticle

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AB - Charge-transfer absorption, electrochemical, and NMR-NOE studies of monomeric and dimeric (ligand-bridged) ruthenium ammine guest interactions with several crown ether hosts show that second-sphere complexation is prevalent in nitromethane as solvent and that complexation or binding constants can be varied by ca. 108-fold by modifying both guest and host properties. For hosts, larger binding constants are obtained with larger macrocycles and with more flexible macrocycles (i.e. dicyclohexano vs dibenzo crowns). For guests, larger binding constants are observed in higher oxidation states and in the presence of strongly electron-withdrawing ancillary ligands. In all cases, binding appears to be driven primarily by ammine hydrogen/ether oxygen (Lewis acid/base) interactions. Evidence is also found, however, for contributions from favorable benzene(crown)/pyridine(complex) interactions and (apparently) benzene(crown) → Ru(III) charge-transfer (donor/acceptor) interactions.

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