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Gas‐phase functionalized carbon‐carbon coupling reactions catalyzed by Ni (II) complexes
Author(s) -
Piacentino Elettra L.,
Rodriguez Edwin,
Parker Kevin,
Gilbert Thomas M.,
O'Hair Richard A. J.,
Ryzhov Victor
Publication year - 2019
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.4360
Subject(s) - chemistry , electrospray ionization , dissociation (chemistry) , catalysis , coupling reaction , nickel , medicinal chemistry , carboxylate , mass spectrometry , density functional theory , yield (engineering) , ion , inorganic chemistry , photochemistry , stereochemistry , computational chemistry , organic chemistry , chromatography , materials science , metallurgy
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 (OOCR 1 )] + (where phen = 1,10‐phenanthroline), were formed by electrospray ionization. Upon collision‐induced dissociation (CID), they extrude CO 2 forming the organometallic cation [(phen)Ni(R 1 )] + , which undergoes gas‐phase ion‐molecule reactions (IMR) with acetate esters CH 3 COOR 2 to yield the acetate complex [(phen)Ni (OOCCH 3 )] + and a C―C coupling product R 1 ‐R 2 . These Ni(II)/phenanthroline‐mediated coupling reactions can be performed with a variety of carbon substituents R 1 and R 2 ( sp 3 , sp 2 , or aromatic), some of them functionalized. Reaction rates do not seem to be strongly dependent on the nature of the substituents, as sp 3 ‐ sp 3 or sp 2 ‐ sp 2 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.