# Copper Sulfide Model Complexes for Small Molecule Activation

> **NIH NIH R01** · UNIVERSITY OF ILLINOIS AT CHICAGO · 2020 · $189,684

## Abstract

Atmospheric concentrations of CO2 and N2O, the #1 and #2 most consequential greenhouse gases on earth,
both are regulated in part by metalloproteins containing multimetallic copper-sulfide active sites. The nature of
multimetallic cooperativity in these active sites and the role of the conserved copper-sulfide structure as it
relates to enzymatic function are poorly understood. The objective of this application is to use synthetic model
studies to understand the role of nature's privileged copper-sulfide cluster motif in facilitating multimetallic
cooperativity associated with multielectron/multiproton regulation of both CO2 and N2O. Our central hypothesis
is that the bridging sulfur atoms both covalently mediate redox coupling of the individual metal sites, and also
participate in covalent activation of the small molecule substrates. Our rationale for pursuing this objective is
that it will inform and motivate future catalyst designs for crucial multielectron redox transformations that
depend on CO2, N2O, and other small-molecule substrates. We will work towards achieving the overall
objective by pursuing the following specific aims: 1) develop synthetic methods for tetracopper, dicopper, and
copper-molybdenum clusters with single sulfur atom bridges; 2) conduct combined spectroscopic-
computational studies of electronic structure across different cluster oxidation states; 3) investigate
stoichiometric and catalytic reactions with CO2, N2O, and related model substrates. The proposed research is
significant because the synthetic difficulty in accessing such model complexes has precluded their careful
study until now, and so our team is in a unique position to make important contributions that advance the field
vertically. This approach is innovative because it gives us a unique ability to address biologically relevant
coordination chemistry questions with structurally faithful model systems constructed through rational design.
Attaining the objective of the proposal will positively impact the chemical community, as
multielectron/multiproton transformations of small molecules are crucial not only to biological systems but also
to many frontier areas including alternative energy conversion and storage.

## Key facts

- **NIH application ID:** 9930087
- **Project number:** 5R01GM116820-05
- **Recipient organization:** UNIVERSITY OF ILLINOIS AT CHICAGO
- **Principal Investigator:** Neal P Mankad
- **Activity code:** R01 (R01, R21, SBIR, etc.)
- **Funding institute:** NIH
- **Fiscal year:** 2020
- **Award amount:** $189,684
- **Award type:** 5
- **Project period:** 2016-08-01 → 2022-05-31

## Primary source

NIH RePORTER: https://reporter.nih.gov/project-details/9930087

## Citation

> US National Institutes of Health, RePORTER application 9930087, Copper Sulfide Model Complexes for Small Molecule Activation (5R01GM116820-05). Retrieved via AI Analytics 2026-05-25 from https://api.ai-analytics.org/grant/nih/9930087. Licensed CC0.

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