Synthesis and structural analysis of cis-bis(1,10-phenanthroline)dicarbonyl ruthenium(II) 1.72-trifluoromethanesulfonate 0.28-hexafluoridophosphate

Ruthenium(II) complexes containing both 1,10-phenanthroline (Phen) and carbonyl (CO) ligands are important molecules for various applications including catalysis. In this work, the molecular structure of [Ru(Phen)2(CO)2]2+ was determined via X-ray diffraction analysis for the first time. The complex exhibits substitutional disorder of one of counter-anions in the asymmetric unit, with different occupancies for CF3SO3- (0.72) and PF6- (0.28). The ruthenium atom is coordinated in a distorted octahedral environment by two carbonyl carbon atoms and four nitrogen atoms from bis-Phen ligands. The cation displays a cis configuration of the carbonyl ligands. Several hydrogen bonds and π-π interactions are present in the crystal. In addition to structural characterization, IR spectral data for the complex is compared with calculated values. These results provide fundamental data for understanding various properties of related ruthenium complexes.

Steric and Electronic Effect of Cp-Substituents on the Structure of the Ruthenocene Based Pincer Palladium Borohydrides

Ruthenocene-based PCPtBu pincer ligands were used to synthesize novel pincer palladium chloride RcF[PCPtBu]PdCl (2a) and two novel palladium tetrahydroborates RcF[PCPtBu]Pd(BH4) (3a) and Rc*[PCPtBu]Pd(BH4) (3b), where RcF[PCPtBu] = κ3-{2,5-(tBu2PCH2)2-C5H2}Ru(CpF) (CpF = C5Me4CF3), and Rc*[PCPtBu] = κ3-{2,5-(tBu2PCH2)2C5H2}Ru(Cp*) (Cp* = C5Me5). These coordination compounds were characterized by X-ray, NMR and FTIR techniques. Analysis of the X-ray data shows that an increase of the steric bulk of non-metalated cyclopentadienyl ring in 3a and 3b relative to non-substituted Rc[PCPtBu]Pd(BH4) analogue (3c; where Rc[PCPtBu] = κ3-{2,5-(tBu2PCH2)2C5H2}Ru(Cp), Cp = C5H5) pushes palladium atom from the middle plane of the metalated Cp ring in the direction opposite to the ruthenium atom. This displacement increases in the order 3c < 3b < 3a following the order of the Cp-ring steric volume increase. The analysis of both X-ray and IR data suggests that BH4 ligand in both palladium tetrahydroborates 3a and 3b has the mixed coordination mode η1,2. The strength of the BH4 bond with palladium atom increases in the order Rc[PCPtBu]Pd(BH4) < Rc*[PCPtBu]Pd(BH4) < RcF[PCPtBu]Pd(BH4) that appears to be affected by both steric and electronic properties of the ruthenocene moiety.

Dichlorido(η6-p-cymene)[tris(2-cyanoethyl)phosphine]ruthenium(II)

The tris(2-cyanoethyl)phosphine (tcep) complex [RuCl2{P(CH2CH2CN)3}(η6-p-cymene)] (p-cymene = p-CH3C6H4iPr) was synthesised by the bridge-splitting reaction of the chlorido-dimer [RuCl2(η6-p-cymene)]2 with tcep. The complex was characterised by a single-crystal X-ray structure determination as well as NMR spectroscopy, ESI mass spectrometry, and microelemental analysis. X-ray crystallography shows the ruthenium atom is coordinated by p-cymene in a η6-fashion, two chlorides and the phosphorus atom of the tcep ligand with the donor set defining a distorted octahedral geometry. The ESI mass spectrometry study reveals that the complex readily forms negative ions [M + Cl]− and [2M + Cl]− by association with a chloride ion.

Ru atom-modified covalent triazine framework as a robust electrocatalyst for selective alcohol oxidation in aqueous electrolytes

The ruthenium atom-modified covalent triazine framework has selective activity for the electrooxidation of alcohol over competitive water oxidation and self-decomposition.

Magnetic properties of small ruthenium clusters in fullerene cage — A DFT study

Encapsulation of small clusters in fullerene cages provides a stable environment for their application in nanoscale functional devices. In this paper, first principles study of Ruthenium as an endohedral dopant in buckminsterfullerene has been carried out using density functional theory. Ruthenium atom has three stable dopant sites inside C 60, with three possible values of magnetic moment (4, 2 and 0 μB). The doping position of Ru atom can be seen to have an effect on HOMO–LUMO gap, formation energy, binding energy and magnetic moment of the fullerene cage. The interaction between Ru and C atoms in different conformations can be explained in terms of Mulliken analysis and density of states analysis. It is also possible to encapsulate more than one Ru atoms in the C 60 cage ( Ru n@ C 60, n = 2–6); encapsulation up to six atoms has been analyzed, after which the process is energetically unfavorable. The geometry of the lowest energy structures, compared to the isolated Ru n clusters, is found to change as a result of encapsulation (e.g., in Ru 3@ C 60 and Ru 5@ C 60). A reduction in magnetic moment of Ru clusters inside fullerene cage as compared to isolated clusters also occurs due to hybridization and confinement effects. The varied magnetic moments of Ru -encapsulated C 60 molecules reveal its applications in molecular magnetic devices and quantum peapods.

Syntheses and Structures of Two Arene-Ruthenium(II) Complexes with Cyclometalating 2-Pyridyl-m-tolyl Ligands

Reactions of [(η6-C6Me6)RuCl2]2 and [(η6-p-cymene)RuCl2]2 with [Hg(ptpy)2] (Hptpy = 2-pyridyl-m-toluene) in THF afforded [{(η6-C6Me6)Ru(ptpy)}2(μ-Hg2Cl6)] 1 and [(η6-pcymene) Ru(ptpy)(HgCl3)] 2, respectively. The crystal structures of complexes 1 and 2 have been determined by single-crystal X-ray diffraction. The ruthenium atom in both molecules 1 and 2 adopts a pseudo octahedral configuration containing a cyclometalated ptpy ligand. The Ru−C(ptpy) and Ru−N bond lengths in 1 are 2.049(3) and 2.089(2) Å, respectively. The corresponding bond lengths for 2 are 2.025(9) and 2.089(7) Å .