Fixation of atmospheric CO[sub 2] by a series of hydroxo complexes of divalent metal ions and the implication for the catalytic role of metal ion in carbonic anhydrase. Synthesis, characterization, and molecular structure of [LM(OH)][sub n] (n = 1 or 2) and LM([mu]-CO[sub 3])ML (M(II) = Mn, Fe, Co, Ni, Cu, Zn; L = HB(3,5-iPr[sub 2]pz)[sub 3])
- Tokyo Inst. of Technology, Yokohama (Japan)
By using the hindered tris(pyrazoly)borate ligand HB(3,5-iPr[sub 2]pz)[sub 3], (hydrotris(3,5-diisopropyl-1-pyrazolyl)-borate), a series of hydroxo complexes of first-row divalent metal ions (Mn (1), Fe (2), Co (3), Ni (4), Cu (5), Zn (6)) was synthesized. X-ray crystallography was applied to 1-5, establishing that all these hydroxo complexes have a dinuclear structure solely bridged with a bis(hydroxo) unit. The structure of 6 was characterized by spectroscopy, which indicates that 6 is monomeric. All these hydroxo complexes were found to react with CO[sub 2], even atmospheric CO[sub 2], to afford [mu]-carbonato dinuclear complexes of Mn (7), Fe (8), Co (9), Ni (10), Cu (11), and Zn (12). The molecular structures of the complexes 8-12 were determined. A variety of coordination modes of the carbonate group was seen. In 10 and 11, the carbonate group is bound to both metal centers bidentately in a symmetric fashion, while in 8 and 9, the carbonate coordination modes are described as an unsymmetric bidentate. The carbonate group in 12 is coordinated to one zinc ion bidentately, but it is bound to the other zinc ion unidentately. From IR data, the coordination mode of the carbonate group in 7 was suggested to be similar to those found in 8 and 9. Thus, the order of the coordination distortions of the carbonate groups in this series of [mu]-carbonato dinuclear complexes is determined. 40 refs., 8 figs., 4 tabs.
- OSTI ID:
- 5834801
- Journal Information:
- Journal of the American Chemical Society; (United States), Vol. 115:13; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
COMPLEXES
CRYSTALLOGRAPHY
MOLECULAR STRUCTURE
SYNTHESIS
BORON COMPLEXES
CARBON DIOXIDE FIXATION
CATALYSIS
COBALT COMPLEXES
COPPER COMPLEXES
ENZYMES
EXPERIMENTAL DATA
INFRARED SPECTRA
IRON COMPLEXES
MANGANESE COMPLEXES
NICKEL COMPLEXES
NUCLEAR MAGNETIC RESONANCE
SPECTROSCOPY
THEORETICAL DATA
ZINC COMPLEXES
DATA
INFORMATION
MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
PROTEINS
RESONANCE
SPECTRA
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400102 - Chemical & Spectral Procedures