TY - JOUR

T1 - Nucleophilic properties of the positively charged metal center in the solid state structure of Palladium(II)-Terpyridine complex

AU - Kostenko, Ekaterina A.

AU - Baykov, Sergey V.

AU - Novikov, Alexander S.

AU - Boyarskiy, Vadim P.

N1 - Publisher Copyright: © 2019 Elsevier B.V.

PY - 2020/1/5

Y1 - 2020/1/5

N2 - Weak intermolecular noncovalent interactions in the solid palladium(II)-terpyridine complex [4'-(4-methoxyphenyl)-2,2':6′,2″-terpyridine]chloridopalladium(II) chloride were studied by XRD method accompanied with appropriate DFT calculations. The complex in the crystal lattice exhibits a double columnar planar structure. Inside the columns, the complex cations are linked by stacking rather than by hydrogen bonding. DFT calculations and topological analysis of the electron density distribution within the formalism of Bader's theory (QTAIM method) were performed for the terpyridine complex model cluster. The calculation data indicate that the columns are interconnected by π-hole···[dz 2-Pd] and π-hole···lp(Cl) interactions. Estimated strength of these noncovalent contacts varies in range 0.5–1.6 kcal/mol. Metal centers are involved in the stacking via dz 2–π noncovalent bonds, which proved to be more preferable than the Pd⋯Pd metallophilic interactions. The electrostatic surface potential calculations demonstrated dz 2nucleophilic properties of the cationic metal center.

AB - Weak intermolecular noncovalent interactions in the solid palladium(II)-terpyridine complex [4'-(4-methoxyphenyl)-2,2':6′,2″-terpyridine]chloridopalladium(II) chloride were studied by XRD method accompanied with appropriate DFT calculations. The complex in the crystal lattice exhibits a double columnar planar structure. Inside the columns, the complex cations are linked by stacking rather than by hydrogen bonding. DFT calculations and topological analysis of the electron density distribution within the formalism of Bader's theory (QTAIM method) were performed for the terpyridine complex model cluster. The calculation data indicate that the columns are interconnected by π-hole···[dz 2-Pd] and π-hole···lp(Cl) interactions. Estimated strength of these noncovalent contacts varies in range 0.5–1.6 kcal/mol. Metal centers are involved in the stacking via dz 2–π noncovalent bonds, which proved to be more preferable than the Pd⋯Pd metallophilic interactions. The electrostatic surface potential calculations demonstrated dz 2nucleophilic properties of the cationic metal center.

KW - DFT

KW - Hirshfeld analysis

KW - Palladium(II)-Terpyridine complex

KW - XRD

KW - π-interactions

UR - https://www.sciencedirect.com/science/article/pii/S0022286019310488

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85071307590&origin=AuthorNamesList&txGid=b591ce83e99f7357ab9a7c3875425d45

UR - http://www.scopus.com/inward/record.url?scp=85071307590&partnerID=8YFLogxK

U2 - 10.1016/j.molstruc.2019.126957

DO - 10.1016/j.molstruc.2019.126957

M3 - Article

VL - 1199

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

M1 - 126957

ER -