Water exchange of the (o-phenylenediamine-N,N,N prime ,N prime -tetraacetato)ferrate(III) complex in aqueous solution as studied by variable-temperature, -pressure, and -frequency oxygen-17 NMR techniques
Journal Article
·
· Inorganic Chemistry; (United States)
- Nagoya Univ. (Japan)
The crystal structure of potassium aqua (o-phenylenediamine-N,N,N{prime},N{prime}-tetraacetato)ferrate(III) dihydrate, (K(Fe(OH{sub 2})-(phdta)){center dot}2H{sub 2}O), has been determined by x-ray crystallography. The central iron(III) ion is seven-coordinate, with one water molecule being hydrated. Water-exchange rates of the iron(III) complex with phdta{sup 4{minus}} in aqueous solution have been studied as a function of temperature and pressure by the oxygen-17 NMR line-broadening method. Activation parameters for water exchange have been determined as follows: k(25 C) = (1.2 {plus minus} 0.2) {times} 10{sup 7} s{sup {minus}1}, {Delta}H{sup {double dagger}} = 26 {plus minus} 3 kJ mol{sup {minus}1}, {Delta}S{sup {double dagger}} = -22 {plus minus} 9 J K{sup {minus}1} mol{sup {minus}1}, and {Delta}V{sup {double dagger}} = 4.6 {plus minus} 0.2 cm{sup 3} mol{sup {minus}1}. The positive activation volume indicates that the water exchange proceeds via a dissociative interchange mechanism. 41 refs., 4 figs., 4 tabs.
- OSTI ID:
- 5641376
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:7; ISSN 0020-1669; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ALKALI METAL COMPOUNDS
AMINES
CRYSTAL STRUCTURE
DATA
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
FERRATES
HYDRATES
HYDROGEN COMPOUNDS
INFORMATION
IRON COMPOUNDS
ISOTOPES
LIGHT NUCLEI
MOLECULAR STRUCTURE
NMR SPECTRA
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
OXYGEN 17
OXYGEN COMPOUNDS
OXYGEN ISOTOPES
POTASSIUM COMPOUNDS
PRESSURE EFFECTS
SPECTRA
STABLE ISOTOPES
TEMPERATURE EFFECTS
TRANSITION ELEMENT COMPOUNDS
WATER
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ALKALI METAL COMPOUNDS
AMINES
CRYSTAL STRUCTURE
DATA
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
FERRATES
HYDRATES
HYDROGEN COMPOUNDS
INFORMATION
IRON COMPOUNDS
ISOTOPES
LIGHT NUCLEI
MOLECULAR STRUCTURE
NMR SPECTRA
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
OXYGEN 17
OXYGEN COMPOUNDS
OXYGEN ISOTOPES
POTASSIUM COMPOUNDS
PRESSURE EFFECTS
SPECTRA
STABLE ISOTOPES
TEMPERATURE EFFECTS
TRANSITION ELEMENT COMPOUNDS
WATER