TY - JOUR

T1 - Palladium(II) complex with tetrahydrobenzoxosine: synthesis, electronic and molecular structures

AU - Bakaev, I. V.

AU - Romashev, N. F.

AU - Komlyagina, V. I.

AU - Abramov, P. A.

AU - Piskunov, A. V.

AU - Gushchin, A. L.

N1 - ACKNOWLEDGMENTS: The authors thank the Ministry of Science and Higher Education of the Russian Federation (project No. 121031700315-2) and the Common Use Center of NIIC SB RAS for the X-ray diffraction experiment, recording IR and 1H NMR spectra, and for providing computing resources of the computing cluster of NIIC SB RAS.

PY - 2022/12/1

Y1 - 2022/12/1

N2 - Interaction of the palladium(II) benzonitrile complex [Pd(PhCN)2Cl2] with glyoxal-bis(2-hydroxy-3,5-di-tert-butylphenyl)imine (H2L) induces intramolecular rearrangement of H2L into the corresponding tetrahydrobenzoxazinobenzoxosine (L′), and the coordination of the latter to Pd(II) leads to the formation of [Pd(L′)Cl2]·(CH3)2CO (1·(CH3)2CO). The crystal structure of this compound is determined by XRD. The Pd atom in the structure occurs in a square planar environment of two Cl atoms and two N atoms of the L′ ligand. Quantum chemical calculations within the density functional theory are conducted; the electronic structure of 1 is studied. The Pd–N and Pd–Cl bonds are shown to be intermediate type bonds. Orbitals of N–Pd–Cl three-center bonds are discovered using the NBO analysis. The formation of such three-center bonds can be represented as a result of the electron density donation from the orbitals of nitrogen lone pairs to the σ* orbitals of Pd–Cl bonds.

AB - Interaction of the palladium(II) benzonitrile complex [Pd(PhCN)2Cl2] with glyoxal-bis(2-hydroxy-3,5-di-tert-butylphenyl)imine (H2L) induces intramolecular rearrangement of H2L into the corresponding tetrahydrobenzoxazinobenzoxosine (L′), and the coordination of the latter to Pd(II) leads to the formation of [Pd(L′)Cl2]·(CH3)2CO (1·(CH3)2CO). The crystal structure of this compound is determined by XRD. The Pd atom in the structure occurs in a square planar environment of two Cl atoms and two N atoms of the L′ ligand. Quantum chemical calculations within the density functional theory are conducted; the electronic structure of 1 is studied. The Pd–N and Pd–Cl bonds are shown to be intermediate type bonds. Orbitals of N–Pd–Cl three-center bonds are discovered using the NBO analysis. The formation of such three-center bonds can be represented as a result of the electron density donation from the orbitals of nitrogen lone pairs to the σ* orbitals of Pd–Cl bonds.

KW - DFT calculations

KW - XRD

KW - coordination compounds

KW - intramolecular rearrangement

KW - palladium

KW - α-diimines

UR - https://www.scopus.com/inward/record.url?eid=2-s2.0-85145402112&partnerID=40&md5=c67b887ad777863e87e6adb3cbb52782

UR - https://www.mendeley.com/catalogue/b3336d96-67be-395d-a62b-21e10b58df59/

U2 - 10.1134/S0022476622120071

DO - 10.1134/S0022476622120071

M3 - Article

VL - 63

SP - 1963

EP - 1972

JO - Journal of Structural Chemistry

JF - Journal of Structural Chemistry

SN - 0022-4766

IS - 12

ER -