Nitrogen-15 NMR studies of tetrazole complexes of pentamminecobalt(III). Implications concerning the transition state for linkage isomerization
- Univ. of Miami, Coral Gables, FL (United States) Los Alamos National Lab., NM (United States)
Synthesis of the N1-bonded (5-methyltetrazolato)pentaamminecobalt(III) complex utilizing sodium azide enriched in [sup 1]N at the terminal nitrogen has produced a complex enriched specifically at the N2 and N4 ring positions. This has permitted the assignment of all four nitrogen signals in the natural-abundance NMR spectrum for a novel chelated amidine complex which is also N1 bonded is reported along with its synthesis and purification. Following the [sup 15]N NMR of the linkage isomerization of the enriched complex in solution to the N2-bonded form has also permitted an [eta][sup 5] and certain [eta][sup 3] transition-state structures to be eliminated from consideration for the isomerization process. The data suggest an [eta][sup 2] transition state is utilized. A subsequent N2-to-N3 isomerization of the N2-bonded complex has also been discovered from the [sup 15]N NMR study. The enrichment study also indicates that previous assignments of ring nitrogen signals N1 and N4 is similar N2-bonded tetrazolato complexes of cobalt(III) may be in error.
- OSTI ID:
- 5771254
- Journal Information:
- Inorganic Chemistry; (United States), Vol. 32:11; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
COBALT COMPLEXES
ISOMERIZATION
LABELLED COMPOUNDS
CHEMICAL PREPARATION
AMINES
AZOLES
NITROGEN 15
NUCLEAR MAGNETIC RESONANCE
REACTION INTERMEDIATES
CHEMICAL REACTIONS
COMPLEXES
HETEROCYCLIC COMPOUNDS
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NITROGEN ISOTOPES
NUCLEI
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
RESONANCE
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation