Ground-state interactions between ruthenium(II)-diimine complexes and phenol and monochlorophenols in aqueous solution

Journal Article · Mon Jun 15 04:00:00 EDT 1998 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic971471y· OSTI ID:642400

Li, C; Hoffman, M Z ^[1]; Pizzocaro, C; Maihot, G; Bolte, M ^[2]

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1. Boston Univ., MA (United States). Dept. of Chemistry
2. Univ. Blaise Pascal, Aubiere (France). Lab. de Photochimie Moleculaire et Macromoleculaire

Ground-state interactions between Ru(bpy){sub 3}{sup 2+} (bpy = 2,2{prime}-bipyridine) or Ru(bpz){sub 3}{sup 2+} (bpz = 2,2{prime}-bipyrazine) and phenol (PhOH) or monochlorophenols (ClPhOH) have been investigated in aqueous (D{sub 2}O) solution by NMR. The upfield shifts of the resonances and the NOE difference spectra of the complexes in the presence of the phenols indicate the presence of offset face-to-face {pi}-stacking interactions between the phenol and the aromatic ligands. Electron withdrawal from the phenol ring by the monochloro substituent and less effective solvation by aqueous (compared to acetonitrile) media favor the interaction. The formation constant for the 1:1 Ru(bpy){sub 3}{sup 2+{minus}} PhOH complex is estimated to be {approximately} 0.01 M{sup {minus}1}; K is smaller for Ru(bpz){sub 3}{sup 2+} than for Ru(bpy){sub 3}{sup 2+}, and it increases for both complexes in the order PhOH < 4-ClPhOH < 3-ClPhOH < 2-ClPhOH.

• OSTI ID: 642400
• Journal Information: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 12 Vol. 37; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
AQUEOUS SOLUTIONS
CHEMICAL SHIFT
CHLORINATED AROMATIC HYDROCARBONS
ENERGY-LEVEL TRANSITIONS
EXPERIMENTAL DATA
GROUND STATES
IMINES
PHENOL
RUTHENIUM COMPLEXES
SOLVATION