Mode of coordination of tris(2-pyridyl)methanol to ruthenium(II): synthetic, spectral, and structural studies of the bis(ligand) species

Journal Article · Wed Jul 15 00:00:00 EDT 1987 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00261a010· OSTI ID:5572105

Keene, F R; Szalda, D J; Wilson, T A

Two forms of the cation bis(tris(2-pyridyl)methanol)ruthenium(II) have been isolated--a yellow species, (Ru((py)/sub 3/COH)/sub 2/)/sup 2 +/ (2), and an orange form in which one ligand is deprotonated, (Ru((py)/sub 3/COH)((py)/sub 3/CO/sup -/))/sup +/ (1). The pK/sub a/ for the ligand deprotonation is 3.78 (+/-0.02) in aqueous 0.1 M KNO/sub 3/ at 25.0/sup 0/C. X-ray structural determinations show coordination occurs in an (N,N',-N'')(N,N',O) mode for both complexes, with the coordinated oxygen atom being the site of the acid/base reactivity. The deprotonated species (1) has a plane of symmetry with Ru-N bond lengths in the range 2.040-2.063 A. The nondeprotonated form (2) has Ru-N bond lengths in the range of 2.046-2.058 A, except for an abnormally short Ru-N bond (2.023 (2) A) trans to the coordinated Ru-OH. Additionally, in 2 the plane of symmetry is lost. In aqueous solution the redox for the Ru(III)/Ru(II) couples are 0.40 (2) and 0.25 V (1) vs. SSCE. The electronic and /sup 13/C NMR spectra are also reported. Crystal parameters for both the protonated and deprotonated form of the named complex are reported. 39 references, 3 figures, 4 tables.

• Research Organization: James Cook Univ. of North Queensland, Townsville, Australia
• DOE Contract Number: AC02-76CH00016
• OSTI ID: 5572105
• Journal Information: Inorg. Chem.; (United States), Vol. 26:14
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
METHANOL
CHEMICAL PREPARATION
MOLECULAR STRUCTURE
ORGANIC NITROGEN COMPOUNDS
RUTHENIUM COMPOUNDS
CARBON 13
EXPERIMENTAL DATA
NMR SPECTRA
ALCOHOLS
CARBON ISOTOPES
DATA
EVEN-ODD NUCLEI
HYDROXY COMPOUNDS
INFORMATION
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
REFRACTORY METAL COMPOUNDS
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation