Crystal Structures of Half-Sandwich Ru(II) Complexes, [(η6-p-Cymene)(3-chloro-6-(1H-pyrazol-1-yl)pyridazine)Ru(X)]BF4, (X = Cl, Br, I)

Herein, we report the synthesis and single-crystal X-ray structures of three (η6-p-cymene)Ru(II) tetrafluoroborate salts, viz., [(η6-p-cymene)(3-chloro-6-(1H-pyrazol-1-yl)pyridazine)Ru(X)]BF4, (X = Cl, Br, I), Ru1-3. They were prepared by the reactions of [(η6-p-cymene)Ru(μ-X)(X)]2, (X = Cl, Br, I) with two-mole equivalents of 3-chloro-6-(1H-pyrazol-1-yl)pyridazine, under inert conditions at ambient temperatures, and subsequently precipitated by the addition of excess BF4− ions. Orange crystalline precipitates were obtained in good yields, from which the respective single crystals for X-ray diffraction analysis were recrystallized by slow evaporation from their methanolic/diethyl ether solutions. The Ru(II) complexes were characterized by various spectroscopic techniques and chemical methods, which included FTIR, 1H/13C NMR, UV-visible absorption, mass spectrometry, and elemental analysis. The molecular structures were solved by single-crystal X-ray crystal diffraction analysis. The complexes crystallized in the monoclinic crystal system in the P21/c (Ru1-2) and P21/n (Ru3) space groups. Density Functionals Theoretical (DFT) calculations were performed in methanol to gain an understanding of the electronic and structural properties of the complexes. Trends in the data metrics were established, and selected data were compared with the diffraction data. The electrophilicity indices of Ru1-3 follow the order Ru3 > Ru2 > Ru1, and the trend is in line with their anticipated order of reactivity towards nucleophiles.