Resonance Raman studies and vibrational analysis of Ni(II) porphyrins
A local coordinate scheme has been established for a 37-atom metalloporphyrin skeleton, which takes into account the phasing of adjacent bond stretches within the pyrrole ring and at the methine bridges. A consistent valence force field has been developed for Ni porpine (NiP), Ni tetraphenylporphine (NiTPP), and Ni octaethylporphyrin (NiOEP) by fitting the observed Raman and IR band frequencies and the {sup 15}N, {sup 13}C, and {sup 2}H isotope shifts with the aid of bond length-force constant relationships. NiP and its isotopomers deuterated at meso (d{sub 4}), pyrrole (d{sub 8}), and meso + pyrrole (d{sub 12}) carbon atoms have been studied by RR and IR spectroscopies. NiTPP and its {sup 15}N{sub 4} (pyrrole), {sup 13}C{sub 4} (methine bridge), d{sub 8} (pyrrole), and d{sub 20} (phenyl) isotopomers have been investigated by RR spectroscopy with variable wavelength excitations in both crystalline and solution phases. NiOEP and its {sup 15}N{sub 4} (pyrrole), d{sub 4} (meso), d{sub 16} (methylene group) isotopomers, as well as d{sub 4} + {sup 15}N{sub 4}, and d{sub 4} + {sup 62}Ni double isotopomers have been systematically studied in solution and in three different crystalline forms by RR spectroscopy with variable wavelength excitations. IR spectra for NiOEP and its NiOEP-d{sup 16} isotopomer are reported.
- Research Organization:
- Princeton Univ., NJ (USA)
- OSTI ID:
- 7165307
- Resource Relation:
- Other Information: Thesis (Ph. D.)
- Country of Publication:
- United States
- Language:
- English
Similar Records
Consistent porphyrin force field. 2. Nickel octaethylporphyrin skeletal and substituent mode assignments from sup 15 N, meso-d sub 4 , and methylene-d sub 16 Raman and infrared isotope shifts
Analysis of a siroheme model compound: Core-size dependence of resonance Raman bands and the siroheme spin state in sulfite reductase
Related Subjects
PORPHYRINS
CHEMICAL ANALYSIS
CARBON 13
DEUTERIUM
METALLOPROTEINS
NITROGEN 15
RAMAN SPECTROSCOPY
TRACER TECHNIQUES
CARBON ISOTOPES
CARBOXYLIC ACIDS
EVEN-ODD NUCLEI
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HYDROGEN ISOTOPES
ISOTOPE APPLICATIONS
ISOTOPES
LASER SPECTROSCOPY
LIGHT NUCLEI
NITROGEN ISOTOPES
NUCLEI
ODD-EVEN NUCLEI
ODD-ODD NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PROTEINS
SPECTROSCOPY
STABLE ISOTOPES
550201* - Biochemistry- Tracer Techniques