Novel Molecules and Solids Derived from the Cyaphide Ion

Indiana University, Bloomington IN

Investigators

Abstract

With the support of the Chemical Synthesis program in the Division of Chemistry, Professor Jose M. Goicoechea of Indiana University will study a new class of molecules and solids derived from diatomic analogs of cyanide. Cyanide is found across many areas of chemistry, ranging from biological enzyme cofactors to custom-made magnetic materials and catalysts. Cyanide salts are routinely used in applications including bulk chemical synthesis, electroplating, metallurgy, and as fumigants and insecticides. By contrast, the chemistry of the heavier phosphorus- and arsenic-containing ions, the cyaphide and cyarside ions, respectively, is unexplored despite the enormous potential they offer for the synthesis of interesting magnetic materials. This proposal will explore the synthesis of several molecular targets that will offer insight into the electronic structure and properties of these new chemical building blocks. Ultimately, this will prove critical for their use in the design of an entirely new family of molecules and coordination polymers that are currently absent in the chemical literature. Student research training (undergraduates, high school and graduate students) and student mentoring are important components of the project, as is the creation of a public-facing internet educational resource for the project. The scientific goal of this proposal is to develop novel organometallic compounds containing cyaphide (CP) and cyarside (CAs) ligands for the transfer of these functional groups through metathesis and cross-coupling reactions. Proof-of-concept research by the Goicoechea group suggests that such species are isolable, and that reagents containing these new ions can be made to transfer these reactive groups to metal centers using simple salt-metathesis reaction protocols. Obtaining organic and transition metal complexes with these CP and CAs groups will allow for comparisons of their molecular structures and chemical reactivities with analogous complexes containing the more common cyanide (CN) functional group. The experimental components of the project will be complemented with and guided by computational chemistry. With these species in hand, the research team will explore the synthesis of multi-metallic compounds with bridging CP/CAs groups to understand how these ions can be used to enhance magnetic communication between metal centers in oligomeric, polymeric and ultimately two- and three-dimensional extended solids. The synthetic protocols that will be developed will ultimately allow access to a new family of coordination compounds related to Prussian blue, a class of solids that have applications in numerous technologically relevant areas, including magnetism, sensing, catalysis, and energy storage. On a longer time scale, such discoveries are expected to benefit a broad range of researchers, particularly those working in materials science. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.