Journal
INORGANIC CHEMISTRY
Volume 41, Issue 18, Pages 4642-4652Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic025616z
Keywords
-
Categories
Funding
- NIGMS NIH HHS [GM 50730] Funding Source: Medline
Ask authors/readers for more resources
A series of ferrous complexes with the pentadentate ligand 2,6-(bis-(bis-2-pyridyl) methoxymethane) pyridine(PY5) was prepared and examined. PY5 binds ferrous iron in a square-pyramidal geometry, leaving a single coordination site accessible for complexation of a wide range of monodentate exogenous ligands: [Fe-II(PY5)(X)](n+), X = MeOH, H2O, MeCN, pyridine, Cl-, OBz(-), N-3(-), MeO-, PhO-, and CN-. The spin-states of these ferrous complexes are extremely sensitive to the nature of the single exogenous ligand; the spectroscopic and structural properties correlate with their high-spin (hs) or low-spin (Is) electronic ground state. Systematic metrical trends within six crystallographic structures clearly indicate a preferred conformational binding mode of the PY5 ligand. The relative binding affinities of the exogenous ligands in MeOH indicate that exogenous ligand charge is the primary determinant of the binding affinity; the [Fe-II(PY5)](2+) unit preferentially binds anionic ligands over neutral ligands. At parity of charge, strong-field ligands are preferentially bound over weak-field ligands. In MeOH, the pK(a) of the exogenously ligated MeOH in [Fe(PY5)(MeOH)](2+) (9.1) limits the scope of exogenous ligands, as strongly basic ligands preferentially deprotonate [Fe(PY5)(MeOH)](2+) to yield [Fe(PY5)(OMe)](1+) rather than ligate to the ferrous center. Exogenous ligation by a strongly basic ligand, however, can be achieved in polar aprotic solvents.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available