Characterization of Cu-ligand bonds in tris-pyrazolylmethane isocyanide copper(I) complexes based upon combined X-ray diffraction and theoretical study

Coumarin Derivative Induced 3D Organo‐Silver(I) Complex with Tandem Hydrazine Detection and 4‐Nitrophenol Catalysis

“…While the fabrication of 2D or 3D organo-silver(I) complexes is very difficult by monodentate ligand. [24][25][26][27][28][29][30][31][32][33][34][35] Furthermore, the preparation of 2D or 3D silver(I) cluster-based silver(I)-organic frameworks remains a challenge due to the complexity and uncertainty of the self-assembly process. Significantly, the key to the formation of 3D organo-silver(I) complexes lies in the choice of the organic ligands, and it is evident that the ligands with multiple active coordination sites are conducive to the formation of 3D networks.…”

Copper(I)-Catalyzed 1,3-Dipolar Cycloaddition of Ketonitrones to Dialkylcyanamides: A Step toward Sustainable Generation of 2,3-Dihydro-1,2,4-oxadiazoles

“…On the other hand, the TSc structures, corresponding to concerted CA, were successfully found for both metal-free and metal-involving reactions ( TSc free and TSc Cu , respectively). The cyclic nature of these transition states (TSs) has been confirmed by the topological analysis of the electron density distribution within the formalism of the quantum theory of atoms in molecules (QTAIM) method 23 (we successfully used this approach in studies of noncovalent interactions and properties of coordination bonds in various transition metal complexes 20,24 ).…”

Copper(II) Prevents the Saccarine-Dialkylcyanamide Coupling by Forming Mononuclear (Saccharinate)(Dialkylcyanamide)copper(II) Complexes

“…In order to obtain additional indirect evidence supporting the blocking role of the copper(II) in the saccharine/cyanamide coupling, we studied the nature of Cu-N cyanamide and Cu-N sac coordination bonds in 1 and carried out an integrated computational study including the full geometry optimization of the model of structure 1 in the gas phase using the appropriate experimental XRD structure as a starting point, the topological analysis of the electron density distribution (QTAIM) [44], the natural bond orbital and charge decomposition analyses (NBO [45] and CDA [46]), and calculation of the vertical total energies for the Cu-N cyanamide and Cu-N sac coordination bond dissociations (see ESI for all details). This approach has already been successfully used by us upon studies of bonding properties in various similar transition metal complexes [20,[47][48][49][50]. The results of our computational study revealed that (i) crystal-packing strongly affects the structural characteristics of 1 in the solid state; (ii) the dialkylcyanamide copper(II) complexes featuring noticeable contribution of the heterocumulene mesomeric form; (iii) Cu-N cyanamide and Cu-N sac coordination bonds in 1 exhibit a single bond character, clearly polarized toward the N atom and almost purely electrostatic; (iv) the {M}←L σ-donation substantially prevails over the {M}→L π-back-donation in both Cu-N cyanamide and Cu-N sac coordination bonds in 1; (v) the calculated vertical total energies (E v ) for the Cu-N cyanamide and Cu-N sac coordination bond dissociation in optimized equilibrium model structure 1 were 43.6 and 156.4 kcal/mol, respectively.…”