Abstract
Abstract Twenty-two substituted pentacyanoferrates(II) with the formula Na3[Fe(CN)5PX3]·2H2O (PX3=phosphine or phosphite) have been prepared by ligand substitution of sodium amminepentacyanoferrate(II). The phosphite complexes show smaller isomer shifts than the phosphine complexes. The phosphine complexes involving an aryl or bulky phosphine exhibit larger quadrupole splitting than the phosphite complexes. These tendencies in M\ddotossbauer parameters are discussed in terms of the π-acceptor capability of the phosphine and phosphite ligands. The linear dependence of the isomer shifts on both CN stretching frequencies and d-d transition energies is interpreted on the basis of the predominance of iron-to-phosphorus π back-donation.
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