Ru-Ru Distance Research Articles

A new mixed-ligand diruthenium(II) compound. Synthesis and characterization of [Ru2Cl(Me2PCH2PMe2)2(PhNpy)2][PBh4

The title compound was prepared by reacting Ru/sub 2/Cl(O/sub 2/CCH/sub 3/)/sub 2/(PhNpy)/sub 2/(PhNHpy) and (dimethylphosphino)methane (dmpm) in the presence of chlorotrimethylsilane in toluene. The compound was isolated as a crystalline mass by cooling a methanolic solution of the complex in the presence of Na(BPh/sub 4/). The crystals of composition (Ru/sub 2/Cl(dmpm)/sub 2/(PhNpy)/sub 2/)(BPh/sub 4/).1.5MeOH belong to the monoclinic system, space group P2/sub 1//n, with the following unit cell dimensions: a = 14.064 (5) A, b = 24.047 (8) A, c = 18.642 (4) A, ..cap alpha.. = ..gamma.. = 90/sup 0/, ..beta.. = 110.52 (2)/sup 0/, V = 5905 (3) A/sup 3/, Z = 4. The cationic species (Ru/sub 2/Cl(dmpm)/sub 2/(PhNpy)/sub 2/)/sup +/ consists of a diruthenium(II) core held by two dmpm and two PhNpy/sup -/ ligands. The orientation of the PhNpy/sup -/ ligands is unidirectional. The ruthenium that is bonded to pyridine nitrogens has an axial Cl/sup -/ ligand while the axial site on the other ruthenium is vacant because of two pendant phenyl rings on the amine nitrogen atoms. The Ru-Ru distance is 2.340 (2) A. The Ru-Cl, average Ru-P, and average Ru-N distances are 2.480 (5) A, 2.396 (5) A, and 2.122 (12) A, respectively. The averagemore » torsion angle in N-Ru-Ru-N and P-Ru-Ru-P is 19.84/sup 0/. The compound is moderately stable in air in the solid state and is soluble in common organic solvents. The complex is paramagnetic and has a magnetic moment of 2.6 ..mu../sub B/ (at 308K), corresponding to two unpaired spins. The metal-metal bond order is 2.0 according to the sigma/sup 2/..pi../sup 4/delta/sup 2/)(delta*..pi..*)/sup 4/ ground-state electronic configuration. 29 references, 4 figures, 3 tables.« less

ChemInform Abstract: ADSORPTION OF RUTHENIUM TETROXIDE ON METAL SURFACES

AbstractDie Wechselwirkung zwischen gasförmigem RuO4 (1.33 kPa, 25°C) und Edelstahl, Ni, Cu und Au führt nach einem Tag zur Bedeckung mit einem schwarzen Ru‐haltigen Belag des Metalls.

Adsorption of ruthenium tetroxide on metal surfaces

Interactions of gaseous RuO/sub 4/ with stainless steel (SUS), Ni, Cu, and Au metals deposit a black Ru-containing substance on the metals. Identification of the deposit was tried. Contrary to the existing theory, no experimental evidence was obtained for the decomposition of RuO/sub 4/ to RuO/sub 2/; the interactions did not liberate oxygen and the resulting deposit was neither RuO/sub 2/ nor oxides of the metals. X-ray analysis and XPS also showed that the deposit was not mixed oxides of Ru and the metals. The deposit showed a very strong reflection on its X-ray diffraction pattern, which gave interplanar spacings of 4.763, 4.690, and 4.745 A for the deposits on Ni, Cu, and SUS metals, respectively. Ruthenium in the deposits was in the IV state. Hydrogen peroxide was produced in the hydrolysis of the deposit. From these results, it was concluded that adsorbed RuO/sub 4/ changed into a modification on the metals: RuO/sub 4/ molecules are linked one another through Ru-O-O-Ru bonds. The interplanar spacings correspond to the Ru-Ru distance of peroxide bonds. The weak ..pi.. bonds of the molecules and their chemisorption contribute to peroxide bond formation. On heating, a large portion of the deposit volatilized above 500/sup 0/C;more » the remainder was reduced to Ru along with oxidation of the substrate metals. 21 references, 3 figures, 3 tables.« less

Synthesis and structure of a binuclear ruthenium 4-chlorobenzamidato complex

The compound Ru 2Cl(4-Cl-C 6H 4CONH) 4 was prepared by reaction of Ru 2Cl(O 2CCH 3) 4 with 4-Cl-C 6H 4CONH 2 at 180°C. Crystals of the composition Ru 2Cl(4-Cl-C 6H 4CONH) 4CH 3OH were obtained by slow diffusion of CH 3OH containing Et 4NCl into a Me 2SO solution of the compound. The structure of the crystalline product, which loses solvent of crystallization on removal from the mother liquor, was solved by X-ray crystallography by mounting a single crystal in a capillary containing the mother liquor. The crystals belong to the space group P1̄ (triclinic crystal system) with a = 12.731(3) Å, b = 14.389(3) Å, c = 12.604(3) Å, α = 103.41(2)°, β = 106.43(2)°, γ = 64.90(2)°, V = 1988.6(8) Å 3 and Z = 2. There are two half ruthenium dimers linked by a Cl atom and an uncoordinated solvent CH 3OH molecule per asymmetric unit. The ruthenium dimers lie on two centers of inversion at 0, 0, 0 and 1/2, 0, 0. The chloride ions bridge dinuclear cations in the crystal, forming infinite zigzag chains. The average Ru-Ru distance is 2.296[1] Å and each ruthenium atom has a RuClN 2O 2 coordination sphere where the average Ru′-Ru-Cl angle is virtually linear (175.68[6]°). The metal oxidation states in the complex are + 2 and + 3, giving an average value of + 2.5. The arrangement of four bridging 4-Cl-benzamidato ligands is of the 2 : 2 type. The average Ru-N, Ru-O, Ru-Cl distances and Ru(1)-Cl(1)-Ru(2) angle are 2.036[6] Å, 2.044[5] Å, 2.583[2] Å and 117.26(8)°, respectively. The IR spectrum of the compound shows two N-H stretches at 3380 and 3340 cm −1. The electronic spectrum of the compound in Me 2SO exhibits bands at 558 nm (ε = 340 M −1 cm −1), 425 nm (1000) and 320 nm (22,700).

Synthesis and Crystal Structure of Undecacarbonyl (triphenylphospine)-triangulo-triruthenium, Ru 3(CO) 11Ph 3P

Irradiation of Ru 3(CO) 12 hexane in the presence of triphenylphosphine gives undecacarbonyl (triphenylphosphine)- triangulo -triruthenium in addition to the previously obtained Ru(CO) 4PPh 3 and Ru(CO) 3(PPh 3) 2. X-Ray structure determination of the cluster compound reveals a single isomer in which there is a triangle of ruthenium atoms with the triphenylphosphine equatorially substituted and all the carbonyl groups terminally sited. The Ru-Ru distances are 2.907(3), 2.876(3) and 2.875(3)Å, with the longest distance cis to the triphenylphosphine ligand. The crystals are monoclinic space group C2/c with a 22.30(2)Å, b 16.34(1)Å, c 17.42(1)Å, B  103.84(4)° and Z  8. The structure was refined to R 7.2% for 1773 observed counter amplitudes.

Carbon compounds of the transition metals : V. The structure of bis(cyclopentadienyldicarbonyl-rutheium)

The structure of bis(cyclopentadienyldicarbonylruthenium) has been determined in the solid at room temperature. The crystals are monoclinic with a = 7.10, b = 12.48, c = 8.04» and β = 104.33°. The cell dimensions, space-group and structure are compared with those of bis(cyclopentadienyldicarbonyliron). The Ru-Ru distance is 2.73 », Ru-C(terminal CO) 1.86 », Ru-C(bridging) CO) 1.99 » and Ru-C(ring) 2.26 ». In the solid structure is centrosymmetrical.