Heterobimetallic catalysts offer large potential for efficient and selective catalysis of a wide range of reactions. Better understanding of these catalytic mechanisms could yield further improvement in their catalytic abilities. Cp(CO)2Fe-Cu(IPr) (IPr = N,N-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) is a catalyst that has been reported to catalyze arene borylation. The catalytic mechanism of this catalyst that had been previously proposed had the initial step being a metal-metal cleavage. However, computational modeling suggested an alternate mechanism that could be more energetically favorable. Rather than a metal-metal cleavage as the initial step, we proposed a photoactivated carbonyl dissociation. To support this proposition, we performed time resolved Fourier transform infrared spectroscopy experiments that found evidence supporting our proposed mechanism. Based on these experimental results, we have proposed a new catalytic cycle. The determination of collisional cross section is a powerful tool in analytical chemistry for distinguishing isomers. Techniques such as ion mobility spectrometry can be used to find the collisional cross section of ions but require specialized equipment. Fourier transform ion cyclotron resonance (FTICR) mass spectrometry is a widely used technique for determining ion mass. A technique known as CRoss sectional Area from Fourier Transform Ion cyclotron resonance (CRAFTI) uses a standard FTICR instrument to measure the collisional cross section of ions. This is done by performing a Fourier transform on the data and measuring the Lorenztian width of the peak at the resonant frequency and relating that to the exponential decay of the signal in the time domain. We developed a new data analysis technique that is able to extract just the signal at the resonant frequency in the time domain and directly fit the exponential decay. This new data analysis technique opens new possibilities for expanding the capabilities of CRAFTI measurements, including simultaneous measurement of isomers and a new experimental technique that could measure ions above the mass limit of traditional CRAFTI measurements.



College and Department

Physical and Mathematical Sciences; Chemistry and Biochemistry



Date Submitted


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Heterobimetallic, catalyst, time resolved, FTIR, FTICR, CRAFTI, Cross Sectional Area