Abstract

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.

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