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Bonding, Metal‐Atom Dynamics and Hyperfine Interactions of η‐Phospholyl‐ and η‐Pentaphospholyliron Complexes
Author(s) -
Herber Rolfe H.,
Nowik Israel,
Loginov Dmitry A.,
Starikova Zoya A.,
Kudinov Alexander R.
Publication year - 2004
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200400210
Subject(s) - chemistry , hyperfine structure , crystallography , mössbauer spectroscopy , atom (system on chip) , metal , quadrupole splitting , electron paramagnetic resonance , atomic orbital , ring (chemistry) , paramagnetism , electron , nuclear magnetic resonance , atomic physics , organic chemistry , physics , quantum mechanics , computer science , embedded system
A number of structurally related sandwich compounds of iron, in which the central metal atom is ligated to rings containing one or five phosphorus atoms, have been investigated by temperature‐dependent 57 Fe Mössbauer spectroscopy, differential scanning calorimetry and single‐crystal X‐ray diffraction. The quadrupole hyperfine interaction at 90 K evidences a linear dependence on the number of ring phosphorus atoms, decreasing by about 0.35 mm·s −1 for each ring carbon atom replaced by P. This effect is directly related to the change in the overlap between metal atom d‐orbitals and ligand 3s,3p or 2s,2p orbitals due to an increase in the respective bond lengths. Several one‐electron oxidation products of these compounds, which are paramagnetic, have also been examined and show spin−lattice relaxation rates which are fast compared to the characteristic Mössbauer timescale of 98 ns at all temperatures above 90 K. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)