Solvent control of orbital mixing and electronic coupling in Ligand-Bridged mixed-valence complexes

Evidence for an intervalence hole-transfer pathway

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Abstract

Solvent-induced electronic effects exist for intervalence charge-transfer reactions involving complexes of the type (2,2′-bipyridine)2ClRuII(pyrazine)Ru III(NH3)4L4+, where L = NH3 or various pyrazyl, pyridyl, or polypyridyl ligands. Specifically the following are found: (1) Mixing between appropriate donor and acceptor metal orbitals can be influenced substantially by the nature of the solvent. (2) The metal-metal interaction energy, H13, is also affected. (3) From the solvent effects, intervalence transfer appears to follow (in part) a hole-transfer pathway.

Original languageEnglish
Pages (from-to)1563-1565
Number of pages3
JournalJournal of the American Chemical Society
Volume112
Issue number4
Publication statusPublished - Feb 14 1990

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Metals
Ligands
Pyrazines
Charge transfer

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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abstract = "Solvent-induced electronic effects exist for intervalence charge-transfer reactions involving complexes of the type (2,2′-bipyridine)2ClRuII(pyrazine)Ru III(NH3)4L4+, where L = NH3 or various pyrazyl, pyridyl, or polypyridyl ligands. Specifically the following are found: (1) Mixing between appropriate donor and acceptor metal orbitals can be influenced substantially by the nature of the solvent. (2) The metal-metal interaction energy, H13, is also affected. (3) From the solvent effects, intervalence transfer appears to follow (in part) a hole-transfer pathway.",
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N2 - Solvent-induced electronic effects exist for intervalence charge-transfer reactions involving complexes of the type (2,2′-bipyridine)2ClRuII(pyrazine)Ru III(NH3)4L4+, where L = NH3 or various pyrazyl, pyridyl, or polypyridyl ligands. Specifically the following are found: (1) Mixing between appropriate donor and acceptor metal orbitals can be influenced substantially by the nature of the solvent. (2) The metal-metal interaction energy, H13, is also affected. (3) From the solvent effects, intervalence transfer appears to follow (in part) a hole-transfer pathway.

AB - Solvent-induced electronic effects exist for intervalence charge-transfer reactions involving complexes of the type (2,2′-bipyridine)2ClRuII(pyrazine)Ru III(NH3)4L4+, where L = NH3 or various pyrazyl, pyridyl, or polypyridyl ligands. Specifically the following are found: (1) Mixing between appropriate donor and acceptor metal orbitals can be influenced substantially by the nature of the solvent. (2) The metal-metal interaction energy, H13, is also affected. (3) From the solvent effects, intervalence transfer appears to follow (in part) a hole-transfer pathway.

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