Synthesis and proton NMR studies of the electronic structure of ferric phosphine porphyrin complexes

Journal Article · Wed Nov 02 00:00:00 EST 1988 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00295a015· OSTI ID:6047183

Simonneaux, G; Sodano, P

The preparation and spectral properties of low-spin ferric phosphine complexes of a series of synthetic and natural porphyrins have been reported. The proton NMR spectra of Fe(TPP)(PMe/sub 3/)/sub 2/ClO/sub 4/ and Fe(TPP)(PMe/sub 3/)(1-Melm)ClO/sub 4/ have been analyzed. The axial ligand hyperfine shifts have been separated into their dipolar and contact contributions by using both the dominant dipolar shifts for certain porphyrin positions and the magnetic anisotropy data derived from low-temperature ESR spectra. The contact shifts are shown to arise primarily from iron ..-->.. phosphine ..pi..* charge transfer. The trimethylphosphine H peak is shown to shift characteristically upfield on going from (Fe(TPP)PMe/sub 32/)/sup +/ to (Fe(TPP)(PMe/sub 3/)(1-MeIm))/sup +/, confirming that this resonance may serve as a new probe for hemoproteins. 25 references, 2 figures, 3 tables.

• Research Organization: Universite de Rennes (France)
• OSTI ID: 6047183
• Journal Information: Inorg. Chem.; (United States), Vol. 27:22
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
IRON COMPLEXES
SYNTHESIS
PHOSPHINES
PORPHYRINS
DEUTERIUM
EXPERIMENTAL DATA
ISOTOPE EFFECTS
NMR SPECTRA
PHOSPHORUS 31
TRACER TECHNIQUES
CARBOXYLIC ACIDS
COMPLEXES
DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE APPLICATIONS
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ODD-ODD NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOSPHORUS COMPOUNDS
PHOSPHORUS ISOTOPES
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation