I will present our work on two chemical reactions. The first, the reaction of Fe³⁺ with RS-, will enable me to highlight the work of my late wife, Michelle Millar, one of the first women chemistry professors. Michelle did live long enough to win this Old Man award, Michelle Introduced the use of Sterically hindered aromatic thiolates, the addition of groups in the 2 and 6 positions dramatically changed the coordination properties of aromatic thiolate ligands. This led to the first [Fe^III(SR)₄]¹- complexes with monodentate thiolate ligands and to [Fe₄S₄(S-2,4,6(i-Pr)₃C₆H₂)₄]^1- which for many years was the only active site analog that was not synthesized by the Holm group. My group extended this work to [Fe^III(SR)₄]¹- complexes with alkyl thiolates Her work was not good enough to get her tenure at the sexist NYU.
The second is the reaction of green vitriol with the lye of blood (Fe2+ with CN-) which was first used in 1704 by Diesbach and Dipple (aka Dr Frankenstein) to synthesize Prussian blue. This the first reaction in synthetic chemistry was not used again to make a new compound for nearly 300 years until we synthesized trans-[Fe(CN)₄(CO)₂]^2- by the reaction of FeCl₂ with 4 equivalents of NaCN in H₂0 as we bubbled through the solution. [Fe(CN)₅(CO)]^3- can be made in a similar room temperature reaction with 5 equivalents of NaCN. These two compounds have recently been Found on a meteorite. Using simple reactions, we have developed a rich coordination chemistry of FeCN complexes.

Dr Stephen A Koch

Professor of Chemisrtry, SUNY Stony Brook

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