Synthesis of iron nitrosyl complexes with carbamate ligands

Synthesis of iron nitrosyl complexes with carbamate ligands Formation of first row transition metal complexes that can bind a nitrosyl group (NO) is of interest for understanding how biological systems reduce atmospheric pollutants, and for future chemical reactions. One approach is to construct complexes containing an ancillary ligand bound to the metal first and add the nitrosyl group second. A second approach is to form an iron nitrosyl complex with intermediate H2O ligands first, followed by addition of an ancillary N,N-diethyldithiocarbamate ligand. This method and complex were previously reported to be air-stable, making the chemistry more accessible than typical procedures in the absence of oxygen and moisture. The current work investigated the various components of the reaction to identify the most robust procedure. FellSO4-7H2O was reacted with NaNO2 in sulfuric acid to form [Fe(NO)(H2O)5]2-, followed by addition of sodium N,N-diethyldithiocarbamate (dtc) to form (dtc)2Fe(NO). Several different trials were conducted by changing the ratios of starting materials to determine the optimal conditions. IR spectroscopy verified the presence of the nitrosyl complex. Additional variants included using Felll starting materials and silver N,N-diethyldithiocarbamate, which both resulted in formation of the desired product. Future work includes further characterization and isolation of the complex in bulk.


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