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A series of trigonal bipyramidal Fe(CO) 4 L complexes has been prepared and characterized by infrared,  57 Fe Mössbauer and  31 P NMR spectroscopy. A linear correlation, with a negative slope, between the CO stretching frequencies and the isomer shifts demonstrates that the triple bond nature of the carbonyl ligands is strengthened with increasing iron-to-phosphorus back donation. The linear dependence of the quadrupole splittings on the isomer shifts with a positive slope has revealed that the σ-donor capability of the phosphine or phosphite ligand is offset by the π-acceptor capability. The formation of Fe(CO) 4 L complexes from the corresponding free ligands is accompanied by a downfield shift of  31 P NMR chemical shifts. The coordination shifts are linearly correlated with the Mössbauer isomer shifts.

Infrared, 57 Fe Mössbauer, and 31 P NMR Spectroscopic Characterization of Fe(CO) 4 L (L = Phosphine and Phosphite)