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Coordination of diatomic ligands to heme: simply CO
Nathan J Silvernail1, Bruce C Noll, Charles E Schulz
1Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556, USA.
Abstract:
The synthesis and molecular structures of three iron(II) porphyrinates with only CO as the axial ligand(s) are reported. Two five-coordinate [Fe(OEP)(CO)] derivatives have Fe-C = 1.7077(13) and 1.7140(10) A, much shorter than those of six-coordinate [Fe(OEP)(Im)(CO)], although nu(C-O) is 1944-1948 cm(-1). The six-coordinate species [Fe(OEP)(CO)2] has also been studied. The competition for pi-back-bonding of two CO ligands leads to Fe-C distance of 1.8558(10) A and nu(C-O) being increased to 2021 cm(-1). The Mössbauer spectrum has a quadrupole splitting constant of 0 mm/s at 4.2 K, indicating high electronic symmetry.
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