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J Am Chem Soc. 2018 Jul 5;140(26):8100-8104. doi: 10.1021/jacs.8b05019. Epub 2018 Jun 22.

A Highly-Reduced Cobalt Terminal Carbyne: Divergent Metal- and α-Carbon-Centered Reactivity.

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Department of Chemistry and Biochemistry , University of California, San Diego , 9500 Gilman Drive, Mail Code 0358 , La Jolla , California 92093-0358 , United States.


Reported here is the isolation of a dianionic cobalt terminal carbyne derived from chemical reduction of an encumbering isocyanide ligand. Crystallographic, spectroscopic and computational data reveal that this carbyne possesses a low-valent cobalt center with an extensively filled d-orbital manifold. This electronic character renders the cobalt center the primary site of nucleophilicity upon reaction with protic substrates and silyl electrophiles. However, reactions with internal alkynes result in [2+2] cycloaddition with the carbyne carbon to form a new C-C bond.


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