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

Journal Article · Wed May 12 04:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00062a021· OSTI ID:6236235

Todd, M D; Dong, Yuhua; Horney, J; Yoon, D I; Hupp, J T ^[1]

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1. Northwestern Univ., Evanston, IL (United States)

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. 10[sup 8]-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) [yields] Ru(III) charge-transfer (donor/acceptor) interactions. 17 refs., 3 figs., 2 tabs.

• OSTI ID: 6236235
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:10; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AMINES
BASES
CHEMICAL EXPLOSIVES
CHEMICAL REACTIONS
COMPLEXES
CROWN ETHERS
ETHERS
EXPLOSIVES
HYDROGEN COMPOUNDS
INORGANIC ACIDS
INTERACTIONS
LEWIS ACIDS
LEWIS BASES
MAGNETIC RESONANCE
NITRO COMPOUNDS
NITROMETHANE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXIDATION
RESONANCE
RUTHENIUM COMPLEXES
SOLVENTS
TRANSITION ELEMENT COMPLEXES
VALENCE