Neutral and cationic half-sandwich arene ruthenium, Cp*Rh and Cp*Ir oximato and oxime complexes: Synthesis, structural, DFT and biological studies

Abstract

Neutral and cationic half-sandwich arene ruthenium, Cp*Rh and Cp*Ir oximato and oxime complexes: Synthesis, structural, DFT and biological studies.

Arene–Ruthenium(II) Complexes Containing 11H-Indeno[1,2-b]quinoxalin-11-one Derivatives and Tryptanthrin-6-oxime: Synthesis, Characterization, Cytotoxicity, and Catalytic Transfer Hydrogenation of Aryl Ketones

“…It should be noted that in most of the structurally characterized arene−ruthenium complexes with heterocyclic oximes, the N,N-coordinated ligands remain neutral 51−54 and so far only one example of deprotonated 2-pyridyl cyanoxime was reported. 51 The interatomic Ru−N distances involving oxime and heterocyclic nitrogen atoms are in the ranges of 2.08−2.10 and 2.12−2.16 Å and somewhat greater than the corresponding values typical for oxime−ruthenium complexes (1.95−2.04 and 1.95−2.08 Å), probably due to bulkiness of the ligands. The interatomic Ru−Cl distances of about 2.40 Å and Ru−C distances in the range 2.17−2.26 Å are close to typically found in arene−ruthenium complexes.…”

“…The other three sites are occupied by a chlorine atom and two nitrogen atoms of the deprotonated oximate ligands coordinated in a bidentate fashion forming a five-membered chelate ring (Figures – ). It should be noted that in most of the structurally characterized arene–ruthenium complexes with heterocyclic oximes, the N,N-coordinated ligands remain neutral − and so far only one example of deprotonated 2-pyridyl cyanoxime was reported …”

Biological assays and theoretical density functional theory calculations of Rh(I), Ir(III), and Ru(II) complexes of chiral phosphinite ligand

“…The highest occupied molecular orbital (HOMOs) and the lowest unoccupied molecular orbitals (LUMOs) are named as frontier molecular orbitals. These orbitals govern the electron‐accepting and the electron‐donating abilities of a molecule, [ 57 ] so they play an important role in the electrical and optical properties, as well as in UV–Vis spectra and chemical reactions. [ 58,59 ] The HOMOs and LUMOs of all complexes are given in Figures 7 and 8.…”

Half‐Sandwich Iridium Complexes Bearing a Diprotic Glyoxime Ligand: Structural Diversity Induced by Reversible Deprotonation

“…Although an umber of protic mono- [11] and dioxime [10,12] complexes with ap iano-stool geometry have been reported, their deprotonation has attracted much less attention. [7,8,[13][14][15] Pioneering work of Kçlle evaluated the pK a values of the rhodium and cobalt analogues of 1 by titration experiments. [9] The diprotic complex 1 smoothly reactedw ith 0.5 equiv of potassium carbonate to afford the oxime-oximato complex [Cp*IrCl(LH)]( 2)a ss hown in Scheme2.…”