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              <p>The base-assisted cyclometallation of 2-phenylpyridine (2-phpyH) by Cp*Co(III) was holistically addressed both theoretically and experimentally. Combined DFT and DLPNO-CCSD(T) methods assisted by QTAIM-based noncovalent interactions plots (NCI plots), interacting quantum atoms (IQA), and local energy decomposition (LED) analyses have been used for a comparative study of the CMD-promoted cyclocobaltation and the parent cycloiridation of the 2-phpyH. Results suggest a remarkable contribution of noncovalent interactions, especially local electrostatic interactions, in the evolution of the reactive site giving a rational for the optimization of cyclocobaltation. The theoretically predicted benefits of using the acetamidate anion as a base is rationalized and verified experimentally. Cobaltacycle [Cp*Co(2-phpy-C,N)I] was efficiently synthesized from the air-stable [Cp*CoI2]2 and 2-phpyH, in the presence of LiNHAc as base in 83% yield whereas with anhydrous NaOAc as base only 12% yield were achieved under similar conditions. By applying the [NHAc] -promoted cyclometallation various cobaltacycles were synthesized, analytically characterized and their structures resolved by X-ray crystallization analysis, confirming the importance of the acetamidate in the base-assisted cyclometallation. Experimental kinetic isotope effect (KIE) studies validated by Bigeleisen equation-based KIE computations confirm that the formation of the agostic transient is indeed the kinetic determining step of the CMD mechanism in dichloromethane. Application of the [Cp*CoI2]2/LiNHAc mixture to the catalysis of the condensation of 1,2-diphenyacetylene to various aromatics reveals the coexistence of two mechanisms, i.e. CMD and electrophilic C-H activation.</p>
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              <addrLine>21 rue de l’École de médecine - 75006 Paris</addrLine>
              <country key="FR"/>
            </address>
            <ref type="url">http://www.sorbonne-universite.fr/</ref>
          </desc>
        </org>
      </listOrg>
      <listOrg type="projects">
        <org type="anrProject" xml:id="projanr-41401" status="VALID">
          <idno type="anr">ANR-14-CE35-0006</idno>
          <idno type="program">Appel à projets générique</idno>
          <orgName>COCOORDCHEM</orgName>
          <desc>Cohesion in Coordination Chemistry</desc>
          <date type="start">2014</date>
        </org>
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