Mechanistic difference of the iron(III) ion complexation in different solvents

Koji Ishihara, Shigenobu Funahashi, Motoharu Tanaka

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

The activation volumes (ΔV) for the complexation of the iron(III) ion with acetohydroxamic acid, 4-isopropyltropolone, and thiocyanate ion in N,N-dimethylformamide (DMF) and dimethyl sulfoxide (Me2SO) were determined by a high-pressure stopped-flow technique. Values of ΔV for the formation of the (acetohydroxamato)iron(III) and (isopropyltropolonato)iron(III) complexes are -0.8 ± 0.2 and 5.0 ± 0.4 cm3 mol-1, respectively, in DMF and 3.0 ± 0.3 and 10.9 ± 1.7 cm3 mol-1 in Me2SO, respectively. For the formation and dissociation of the 1:1 (isothiocyanato)iron(III) complex in Me2SO, the ΔV values are 3.3 ± 0.6 and -8.5 ± 1.4 cm3 mol-1, respectively. The change in the sign of ΔV is interpreted on the basis of relative bulkiness of both the entering ligand and the coordinated solvent molecule.

Original languageEnglish
Pages (from-to)3589-3592
Number of pages4
JournalInorganic Chemistry
Volume22
Issue number24
Publication statusPublished - 1983
Externally publishedYes

Fingerprint

Complexation
Iron
Ions
iron
ions
Dimethylformamide
Dimethyl Sulfoxide
Chemical activation
activation
dissociation
Ligands
ligands
acids
Molecules
molecules

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Mechanistic difference of the iron(III) ion complexation in different solvents. / Ishihara, Koji; Funahashi, Shigenobu; Tanaka, Motoharu.

In: Inorganic Chemistry, Vol. 22, No. 24, 1983, p. 3589-3592.

Research output: Contribution to journalArticle

Ishihara, Koji ; Funahashi, Shigenobu ; Tanaka, Motoharu. / Mechanistic difference of the iron(III) ion complexation in different solvents. In: Inorganic Chemistry. 1983 ; Vol. 22, No. 24. pp. 3589-3592.
@article{022b8766edb543679280c2f27fc3a5fe,
title = "Mechanistic difference of the iron(III) ion complexation in different solvents",
abstract = "The activation volumes (ΔV‡) for the complexation of the iron(III) ion with acetohydroxamic acid, 4-isopropyltropolone, and thiocyanate ion in N,N-dimethylformamide (DMF) and dimethyl sulfoxide (Me2SO) were determined by a high-pressure stopped-flow technique. Values of ΔV‡ for the formation of the (acetohydroxamato)iron(III) and (isopropyltropolonato)iron(III) complexes are -0.8 ± 0.2 and 5.0 ± 0.4 cm3 mol-1, respectively, in DMF and 3.0 ± 0.3 and 10.9 ± 1.7 cm3 mol-1 in Me2SO, respectively. For the formation and dissociation of the 1:1 (isothiocyanato)iron(III) complex in Me2SO, the ΔV‡ values are 3.3 ± 0.6 and -8.5 ± 1.4 cm3 mol-1, respectively. The change in the sign of ΔV‡ is interpreted on the basis of relative bulkiness of both the entering ligand and the coordinated solvent molecule.",
author = "Koji Ishihara and Shigenobu Funahashi and Motoharu Tanaka",
year = "1983",
language = "English",
volume = "22",
pages = "3589--3592",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "24",

}

TY - JOUR

T1 - Mechanistic difference of the iron(III) ion complexation in different solvents

AU - Ishihara, Koji

AU - Funahashi, Shigenobu

AU - Tanaka, Motoharu

PY - 1983

Y1 - 1983

N2 - The activation volumes (ΔV‡) for the complexation of the iron(III) ion with acetohydroxamic acid, 4-isopropyltropolone, and thiocyanate ion in N,N-dimethylformamide (DMF) and dimethyl sulfoxide (Me2SO) were determined by a high-pressure stopped-flow technique. Values of ΔV‡ for the formation of the (acetohydroxamato)iron(III) and (isopropyltropolonato)iron(III) complexes are -0.8 ± 0.2 and 5.0 ± 0.4 cm3 mol-1, respectively, in DMF and 3.0 ± 0.3 and 10.9 ± 1.7 cm3 mol-1 in Me2SO, respectively. For the formation and dissociation of the 1:1 (isothiocyanato)iron(III) complex in Me2SO, the ΔV‡ values are 3.3 ± 0.6 and -8.5 ± 1.4 cm3 mol-1, respectively. The change in the sign of ΔV‡ is interpreted on the basis of relative bulkiness of both the entering ligand and the coordinated solvent molecule.

AB - The activation volumes (ΔV‡) for the complexation of the iron(III) ion with acetohydroxamic acid, 4-isopropyltropolone, and thiocyanate ion in N,N-dimethylformamide (DMF) and dimethyl sulfoxide (Me2SO) were determined by a high-pressure stopped-flow technique. Values of ΔV‡ for the formation of the (acetohydroxamato)iron(III) and (isopropyltropolonato)iron(III) complexes are -0.8 ± 0.2 and 5.0 ± 0.4 cm3 mol-1, respectively, in DMF and 3.0 ± 0.3 and 10.9 ± 1.7 cm3 mol-1 in Me2SO, respectively. For the formation and dissociation of the 1:1 (isothiocyanato)iron(III) complex in Me2SO, the ΔV‡ values are 3.3 ± 0.6 and -8.5 ± 1.4 cm3 mol-1, respectively. The change in the sign of ΔV‡ is interpreted on the basis of relative bulkiness of both the entering ligand and the coordinated solvent molecule.

UR - http://www.scopus.com/inward/record.url?scp=0010613970&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0010613970&partnerID=8YFLogxK

M3 - Article

VL - 22

SP - 3589

EP - 3592

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 24

ER -