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Gas‐phase functionalized carbon‐carbon coupling reactions catalyzed by Ni (II) complexes |
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| Authors: | Elettra L. Piacentino Edwin Rodriguez Kevin Parker Thomas M. Gilbert Richard A. J. O'Hair Victor Ryzhov |
| Affiliation: | 1. Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL, 60115 USA;2. https://orcid.org/0000-0002-8044-0502;3. Bio 21 Institute and School of Chemistry, University of Melbourne, Melbourne, Victoria, 3010 Australia;4. Victor Ryzhov, Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA.;5. Richard A. J. O'Hair, Bio 21 Institute and School of Chemistry, University of Melbourne, Melbourne, Victoria 3010, Australia.;6. https://orcid.org/0000-0001-6041-9821;7. Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL, 60115 USADedicated to Prof. Catherine Fenselau in celebration of her seminal contributions to bioanalytical mass spectrometry and in deep appreciation of her mentorship and guidance. Victor Ryzhov, Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA. |
| Abstract: | Gas‐phase C―C coupling reactions mediated by Ni (II) complexes were studied using a linear quadrupole ion trap mass spectrometer. Ternary nickel cationic carboxylate complexes, [(phen)Ni (OOCR1)]+ (where phen = 1,10‐phenanthroline), were formed by electrospray ionization. Upon collision‐induced dissociation (CID), they extrude CO2 forming the organometallic cation [(phen)Ni(R1)]+, which undergoes gas‐phase ion‐molecule reactions (IMR) with acetate esters CH3COOR2 to yield the acetate complex [(phen)Ni (OOCCH3)]+ and a C―C coupling product R1‐R2. These Ni(II)/phenanthroline‐mediated coupling reactions can be performed with a variety of carbon substituents R1 and R2 (sp3, sp2, or aromatic), some of them functionalized. Reaction rates do not seem to be strongly dependent on the nature of the substituents, as sp3‐sp3 or sp2‐sp2 coupling reactions proceed rapidly. Experimental results are supported by density functional theory calculations, which provide insights into the energetics associated with the C―C bond coupling step. |
| Keywords: | C― C coupling decarboxylation ion‐molecule reactions Ni (II) catalysis |