Manipulating Ligand Fields: Can 1st Row Transition Elements Behave as Their 2nd Row Congeners?

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The Chemical Synthesis Program of the Division of Chemistry supports Prof. Peter T. Wolczanski, Chemistry Department, Cornell University, for research into imparting properties associated 2nd transition elements to 1st transition series elements. Many important commercial applications of transition metals use expensive, heavier elements that often pose significant health risks. This proposal seeks replacement compounds that contain earth abundant, less toxic, base- metals, hence first row transition metal complexes are the general focus. A significant product of this research is the human element; the generation of independent, versatile PhDs capable of adapting to a challenging market, which encompasses academic, industrial, government, and entrepreneurial occupations. The work will be disseminated through the scientific literature, in professional meetings, in the patent literature should the situation arise, and via other appropriate public forums. Iron is targeted specifically for utilization in olefin metathesis, and "redox non-innocent" (RNI) organic ligands are also featured, due to their ability to enhance chemical reactivity by giving or taking electrons from the metal. Special emphasis is given to compounds and transformations that pertain to future catalytic and environmentally friendly applications. A fundamental understanding of ionic vs. covalent character is naturally addressed via the studies of RNI, and comparisons of transition metal reactivity. The scientific product of the research is the expansion of general knowledge regarding first row transition metal electronic structure, and concomitant reactivity. A desktop methodology for determining chemical stability, which provides insight into differences between first row transition metals and their heavier congeners, is under development, thus providing an additional pedagogical product.