Synthesis, Structure, and Characterization of Dichloro‐(1‐Benzyl‐4‐Acetato‐1,4,7‐Triazacyclononane)Iron(III) | Zendy

Malkhasian Aramice Y. S. | Zendy; Finch Maila E. | Zendy; Pawlak Piotr L. | Zendy; Anderson Jay M. | Zendy; Brennessel William W. | Zendy; Chavez Ferman A. | Zendy

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Synthesis, Structure, and Characterization of Dichloro‐(1‐Benzyl‐4‐Acetato‐1,4,7‐Triazacyclononane)Iron(III)

Author(s) -

Malkhasian Aramice Y. S.,

Finch Maila E.,

Pawlak Piotr L.,

Anderson Jay M.,

Brennessel William W.,

Chavez Ferman A.

Publication year - 2008

Publication title -

zeitschrift für anorganische und allgemeine chemie

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.354

H-Index - 66

eISSN - 1521-3749

pISSN - 0044-2313

DOI - 10.1002/zaac.200800014

Subject(s) - chemistry , acetonitrile , carboxylate , aqueous solution , ligand (biochemistry) , electron paramagnetic resonance , amine gas treating , inorganic chemistry , electrochemistry , medicinal chemistry , titration , oxidation state , octahedron , crystallography , stereochemistry , crystal structure , organic chemistry , metal , nuclear magnetic resonance , biochemistry , physics , receptor , electrode

The synthesis, structure and aqueous solution behavior of [FeL 1 Cl 2 ] ( 1 , L 1 = 1‐benzyl‐4‐acetato‐1,4,7‐triazacyclononane) is reported. The X‐ray structure of 1 reveals iron(III) in distorted octahedral geometry bonded to three amine nitrogen atoms and one carboxylate oxygen atom along with two cis chloride atoms. Electrochemical measurements of 1 in acetonitrile indicate that E 1/2 = −200 mV vs Ag/AgCl. The stability of the +3 oxidation state is attributed to the hard N amine and carboxylate ligand donors. In acetonitrile, 1 is mononuclear and has an S = 5/2 spin state. The presence of a μ ‐oxo bridge upon dissolution of 1 in water is supported by EPR and solution magnetic susceptibility NMR studies. pH‐metric titrations and UV‐vis studies indicate the presence of a total of four acidic protons. At low pH, L 1 (OH 2 )Fe‐O‐Fe(OH 2 )L 1 is proposed to be stabilized while at high pH, L 1 (OH)Fe‐O‐Fe(OH)L 1 is suggested to persist.

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