Unusual coordination and metal-ligand geometry of a vanadyl porphyrin in aqueous solution

Journal Article · Thu Aug 04 04:00:00 EDT 1983 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100239a008· OSTI ID:5559378

Shelnutt, J A; Dobry, M M

Vanadyl uroporphyrin I in aqueous alkaline solution has considerably modified absorption and resonance Raman spectra when compared with vanadyl porphyrins in organic solvents or in the crystalline state. Under these latter conditions vanadyl porphyrins are known to contain 5-coordinate, out-of-plane vanadium(IV). The unusual spectra of vanadyl uroporphyrin in water can be converted to spectra typical of the 5-coordinate vanadyl prophyrins by formation of ..pi..-..pi.. complexes or by ..pi..-..pi.. dimerization. Because ..pi..-..pi.. complex formation and dimerization block addition of an axial sixth ligand a 6-coordinate, in-plane dihydroxide vanadium(IV) uroporphyrin complex is indicated. This hypothesis is consistent with an analysis of the frequencies of the core-size marker lines of metalloporphyrins indicating expansion of the metal core by 0.03 to 0.04 A in V(OH)/sub 2/UroP. 5 figures.

• Research Organization: Sandia National Labs., Albuquerque, NM
• DOE Contract Number: AC04-76DP00789
• OSTI ID: 5559378
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 87:16; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500 -- Photochemistry
ABSORPTION SPECTRA
ADDITIVES
ALKALI METAL COMPOUNDS
AQUEOUS SOLUTIONS
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
COMPLEXES
DATA
DIMERIZATION
DISPERSIONS
ELECTROMAGNETIC RADIATION
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
HYDROXIDES
INFORMATION
IONIZATION
LASER RADIATION
LIGANDS
MIXTURES
MOLECULAR STRUCTURE
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PHENANTHROLINES
PHOTOIONIZATION
POLYMERIZATION
PORPHYRINS
RADIATIONS
SODIUM COMPOUNDS
SODIUM HYDROXIDES
SOLUTIONS
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
VANADIUM COMPLEXES
VANADIUM COMPOUNDS
VANADIUM HYDROXIDES
WATER