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Spectral, crystallographic, theoretical, and catalytic activity studies of the PdII complexes in different coordination modes of benzoylthiourea ligand

2022; Elsevier BV; Volume: 1269; Linguagem: Inglês

10.1016/j.molstruc.2022.133839

1872-8014

Ümmühan Solmaz, Hakan Arslan,

Organometallic Compounds Synthesis and Characterization

• Two Pd II complexes in different coordination modes were obtained. • The molecular geometry of [Pd II (L-κ 2 S,O) 2 ] was optimized by using DFT/B3LYP method. • The complexes showed excellent efficiency towards Suzuki-Miyaura C-C reaction. • Hirshfeld surface and energy framework analysis were carried out. • Mulliken population analysis and natural population analysis were carried out Syntheses of neutral monodentate dichloro bis [ N ‐(diethylcarbamothioyl)‐4‐fluorobenzamido-κS] palladium(II), [Pd II Cl 2 (LH-κS) 2 ] and anionic bidentate bis [ N ‐(diethylcarbamothioyl)‐4‐fluorobenzamido-κ 2 O,S] palladium(II), [Pd II (L-κ 2 S,O) 2 ] complexes of N ‐(diethylcarbamothioyl)‐4‐fluorobenzamide (LH) ligand is reported. While [Pd II Cl 2 (LH-κS) 2 ] was obtained by reaction between PdCl 2 and LH in acetonitrile solution as a single crystal form, [Pd II (L-κ 2 S,O) 2 ] was formed recrystallization of [Pd II Cl 2 (LH-κS) 2 ] in dichloromethane: ethanol solvent mixture as powder form. The Pd II complexes were characterized by elemental analysis, FT-IR, 1 H NMR, and 13 C NMR spectral measurements. Furthermore, the molecular structure of [Pd II Cl 2 (LH-κS) 2 ] was defined by single crystal X-ray diffraction, and the result obtained was also confirmed by spectral data. The optimized molecular geometry of the ligand and [Pd II Cl 2 (LH-κS) 2 ] complex was obtained by density functional theory calculation at the B3LYP/6-311G(d,p) and LanL2DZ level of theory, respectively. We found that the optimized geometrical parameters agree very well with the experimental one. Therefore, we used the same theoretical level (B3LYP/LanL2DZ) for the [Pd II (L-κ 2 S,O) 2 ] which is a powder form, not a single crystal form. The energies of frontier molecular orbitals ( E HOMO and E LUMO ), energy band gap, and quantum molecular descriptors of the prepared compounds were calculated. Information about the site of chemical reactivity, charge density distribution, the size, and shape of the molecules was obtained by mapping with molecular electrostatic potential (MEP). NBO analysis was applied for the investigation of intra and inter-molecular bonding and conjugative interaction in molecular systems. The Mulliken and natural population analyses were used to predict positive and negative charges on every atom in the molecules. Hirshfeld surface analysis and 2D fingerprint plots were applied to visualize and quantify intermolecular interactions and packing modes in the supramolecular structure. The Coulomb interaction, dispersion, and total energy calculations were used to visualize and analyze the three-dimensional figures of the crystal lattice. Furthermore, the catalytic efficiencies of both palladium complexes have been confirmed in the Suzuki-Miyaura C-C reaction using a very low 0.01 mol% catalyst loading. Two Pd II complexes in different coordination modes of 4-fluoro substituted benzoylthiourea were obtained and fully characterized by the spectral methods. LH and [Pd II Cl 2 (LH-κS) 2 ] are compared using single-crystal X-ray analysis and DFT/B3LYP/6-311G(d,p) and LanL2DZ methods, respectively. The molecular geometry of [Pd II (L-κ 2 S,O) 2 ] was optimized by using the DFT/B3LYP method with the LanL2DZ basis set. The molecular electrostatic potential map, Mulliken and natural atomic charges, and frontier molecular orbitals analysis of the compounds were obtained with the same level of theory. Hirshfeld surface analysis and 2D fingerprint plots were carried out to investigate the intermolecular interactions. The catalytic efficiencies of the Pd II complexes were verified with the Suzuki-Miyaura cross-coupling reaction.