/sup 13/C NMR study of (meso-2,3-butanediaminetetraacetato)nickelate(II)
Journal Article
·
· Inorg. Chem.; (United States)
The temperature and pH dependences of the /sup 13/C NMR spectrum of the paramagnetic nickel(II) complex with meso-2,3-butanediaminetetraacetic acid are reported and interpreted to indicate that the ligand acts as a hexadentate coordinator at all temperatures accessible in deuteriated water and over the pH range from 1 to 13. Less than 1% of the ligands act as pentadentate coordinators. The incomplete coalescence of acetate resonances coupled with concurrent complete coalescence of backbone resonances is interpreted to indicate that ..delta.. reversible lambda conversion proceeds rapidly at moderate (ca 70/sup 0/C) temperatures through a symmetrical intermediate formed without bond breaking, while nitrogen inversion, which requires nickel-nitrogen bond rupture, is slow over the accessible temperature range (<109 /sup 0/C). The previously proposed mechanism for the racemization of Ni(EDTA)/sup 2 -/, which required the presence of an uncoordinated ligand arm, is probably incorrect. A mechanism is proposed that explains the previous and current data without invoking action by a free acetate arm. The meso-BDTA chelate ring is found to be more puckered than the chelate ring of EDTA. The pentadentate form of meso-BDTA is destabilized by at least 8 kJ mol/sup -1/ relative to the pentadentate form of EDTA because of steric interaction between a free carboxylate and the axial methyl substituent. 21 references, 4 figures, 1 table.
- Research Organization:
- Univ. of New Orleans, LA
- OSTI ID:
- 5522795
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:17; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Journal Article
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OSTI ID:4816897
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Thu Jan 07 23:00:00 EST 1988
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OSTI ID:6333917
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· Inorganic Chemistry; (United States)
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OSTI ID:6725282
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ALKANES
BUTANE
CARBON 13
CARBON ISOTOPES
COMPLEXES
DATA
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
ISOTOPES
LIGHT NUCLEI
MOLECULAR STRUCTURE
NICKEL COMPLEXES
NMR SPECTRA
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PH VALUE
SPECTRA
STABLE ISOTOPES
TEMPERATURE DEPENDENCE
TRANSITION ELEMENT COMPLEXES
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ALKANES
BUTANE
CARBON 13
CARBON ISOTOPES
COMPLEXES
DATA
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
ISOTOPES
LIGHT NUCLEI
MOLECULAR STRUCTURE
NICKEL COMPLEXES
NMR SPECTRA
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PH VALUE
SPECTRA
STABLE ISOTOPES
TEMPERATURE DEPENDENCE
TRANSITION ELEMENT COMPLEXES