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Eight new ruthenium and five new osmium p-cymene half-sandwich complexes have been synthesized, characterized and evaluated for antimalarial activity. All complexes contain ligands that are based on a 4-chloroquinoline framework related to the antimalarial drug chloroquine. Ligands HL(1-8) are salicylaldimine derivatives, where HL(1) = N-(2-((2-hydroxyphenyl)methylimino)ethyl)-7-chloroquinolin-4-amine, and HL(2-8) contain non-hydrogen substituents in the 3-position of the salicylaldimine ring, viz. F, Cl, Br, I, NO2, OMe and (t)Bu for HL(2-8), respectively. Ligand HL(9) is also a salicylaldimine-containing ligand with substitutions in both 3- and 5-positions of the salicylaldimine moiety, i.e. N-(2-((2-hydroxy-3,5-di-tert-butylphenyl)methyl-imino)ethyl)-7-chloroquinolin-4-amine, while HL(10) is N-(2-((1-methyl-1H-imidazol-2-yl)methylamino)ethyl)-7-chloroquinolin-4-amine) The half sandwich metal complexes that have been investigated are [Ru(η(6)-cym)(L(1-8))Cl] (Ru-1-Ru-8, cym = p-cymene), [Os(η(6)-cym)(L(1-3,5,7))Cl] (Os-1-Os-3, Os-5, and Os-7), [M(η(6)-cym)(HL(9))Cl2] (M = Ru, Ru-HL(9); M = Os, Os-HL(9)) and [M(η(6)-cym)(L(10))Cl]Cl (M = Ru, Ru-10; M = Os, Os-10). In complexes Ru-1-Ru-8 and Ru-10, Os-1-Os-3, Os-5 and Os-7 and Os-10, the ligands were found to coordinate as bidentate N,O- and N,N-chelates, while in complexes Ru-HL(9) and Os-HL(9), monodentate coordination of the ligands through the quinoline nitrogen was established. The antimalarial activity of the new ligands and complexes was evaluated against chloroquine sensitive (NF54 and D10) and chloroquine resistant (Dd2) Plasmodium falciparum malaria parasite strains. Coordination of ruthenium and osmium arene moieties to the ligands resulted in lower antiplasmodial activities relative to the free ligands, but the resistance index is better for the ruthenium complexes compared to chloroquine. Overall, osmium complexes appeared to be less active than the corresponding ruthenium complexes.

A series of four new analogue phases Ca 2 M 2 X (M = Pd, Pt and X = Al, Ge) were prepared by direct combination of the respective elements in stoichiometric mixtures at high temperature in order to analyze the impact of valence electron count (vec) and electronegativity differences (Δχ) on the structure selection and stability. Their crystal structures, as determined from single-crystal X-ray diffraction data, correspond to two different but closely related structure types. The first compound, Ca 2 Pd 2 Ge (I), is an unprecedented ternary ordered variant of the Zr 2 Al 3 -type (orthorhombic, Fdd2). The three other phases, Ca 2 Pt 2 Ge (II), Ca 2 Pd 2 Al (III) and Ca 2 Pt 2 Al (IV), adopt the Gd 2 Ge 2 Al-type structure (monoclinic, C2/c). All title structures feature linear chains of the noble metals (Pd or Pt). The Pd linear chains in I are undistorted with equidistant Pd···Pd atoms, whereas the metal chains in II-IV are pairwise distorted, resulting in short connected {Pd 2 } or {Pt 2 } dumbbells that are separated by longer M···M contacts. The occurrence and magnitude of the pairing distortion in these chains are controlled by the vec and the Δχ between the constituent elements, a result which is supported by analysis of the calculated Bader effective charges. The metal chains act as charge modulation units, critical for the stability and the electronic flexibility of the structures by an adequate adjustment of the metal-metal bond order to both the vec and the degree of charge transfer. Thus, Ca 2 Pd 2 Ge (28 ve/f.u) is a Zintl-like, charge optimized phase with formally zerovalent Pd atoms forming the undistorted metal chains; semimetallic properties are predicted by TB-LMTO calculations. In contrast, the isoelectronic Ca 2 Pt 2 Ge is predicted to be a good metal with the Fermi level located at a local maximum of the DOS, a fingerprint of potential electronic instability. This is due to greater charge transfer to the more electronegative Pt atoms forming the metal chains and probably to packing frustration in the well packed structure that may prevent a larger distortion of the Pt chains. However, the instability is suppressed in the aliovalent but isostructural phases Ca 2 M 2 Al (27 ve/f.u) with an enhancement of the pairing distortion within the metal chains but lower M-M bond order. Further reduction of the vec as in Ca 2 M 2 Cd (26 ve/f.u) may induce a transition toward the more geometrically flexible W 2 CoB 2 -type with a low dimensional structure, to create more room for a larger distortion of the metal chain as dictated by the shortage of valence electrons. ABSTRACT: A series of four new analogue phases Ca 2 M 2 X (M = Pd, Pt and X = Al, Ge) were prepared by direct combination of the respective elements in stoichiometric mixtures at high temperature in order to analyze the impact of valence electron count (vec) and electronegativity differences (Δχ) on the structure selection and stability. Their crystal structures, as determined from single-crystal X-ray diffraction data, correspond to two ...

Exploratory synthesis in the area of polar intermetallics has yielded a rich variety of structures that offer clues into the transition in bonding between Zintl and Hume-Rothery phases. In this article, we present a bonding analysis of one such compound, Ca 10 Pt 7 Si 3 , whose large Ca content offers the potential for negative formal oxidation states on the Pt. The structure can be divided into a sublattice of Ca cations and a Pt-Si polyanionic network built from Pt 7 Si 3 trefoil units linked through Pt-Pt contacts of 3.14 Å. DFT-calibrated Hückel models reveal that the compound adheres well to a Zintl-like electron counting scheme, in which the Pt-Si and Pt-Pt contacts are equated with two-center two-electron bonds. The experimental electron count is in excess of that predicted by 2%, a discrepancy which is attributed to the electron transfer from the Ca to the Pt-Si network being incomplete. For the Pt-Pt contacts, the occupancy of the bonding orbitals is dependent on the participation of the surrounding Ca atoms in bridging interactions. This use of multi-center interactions isolobal to classical two-center two-electron bonds may illustrate one path by which the bonds delocalize as one moves from the Zintl phases toward the Hume-Rothery domain.