118018-87-4

Upstream product

• 17084-13-8 potassium hexafluorophosphate 
• 65-85-0 benzoic acid 
• 532-32-1 sodium benzoate 
• 118018-83-0 {(1,4,7-trimethyl-1,4,7-triazacyclononane)RuCl₃}*H₂O 

Relevant academic research and scientific papers

New (μ-oxo)bis(μ-carboxylato)diruthenium(III) complexes containing 1,4,7-trimethyl-1,4,7-triazacyclononane ligands

Treatment of [(Me3tacn)RuCl3·H2O] (Me3tacn = 1,4,7-trimethyl-1,4,7-tri-azacyclononane) with substituted benzoic acid or phenylacetic acid, in water in the presence of potassium hexafluorophosphate gave a series of cationic dinuclear Ru(III)–Ru(III) (μ-oxo)bis(μ-carboxylato) complexes [(Me3tacn)2Ru2(μ-O)(μ-OOCR)2](PF6)2 (R = Ph, 1; -py, 2; -C6H4-2-Cl, 3; -C6H3-2,4-Cl2, 4; -CH2C6H4-2-CH3, 5; -CH2C6H4-4-CH3, 6; -CH2C6H4-4-OCH3, 7; -CH2C6H4-4-Cl, 8). All complexes are well characterized by infrared, UV/Vis and mass spectroscopies, and their electrochemical properties were also investigated. The molecular structures of 1, 2·2C3H6O, 5·2C3H6O, 7 and 8 have been also established by single-crystal X-ray diffraction. The photocatalytic properties for H2 evolution by water splitting of complexes 1, 2, 3, 5, and 7 were also investigated in the paper.

(μ-hydroxo)bis(μ-carboxylato)diruthenium and (μ-Oxo)bis(μ-carboxylato)diruthenium complexes containing weak intramolecular Ru?Ru interactions

The hydrolysis reaction of [LRuCl3]·H2O (L represents 1,4,7-trimethyl-1,4,7-triazacyclononane, C9H21N3) in aqueous solution (pH ≈ 7) containing a variety of carboxylic acids yields purple, diamagnetic (μ-oxo)bis(μ-carboxylato)diruthenium(III) dications where each ruthenium is capped by a tridentate cyclic amine L. The crystal structure of [L2RuIII2(μ-O)(μ-CH3CO 2)2](PF6)2· 0.5H2O has been determined by X-ray crystallography. Crystal data: orthorhombic; Ibca (D2h27, No. 73); a = 13.631 (4), b = 14.992 (8), c = 35.465 (8) A?; V = 7247.5 A?3; ρcalcd = 1.79 g/cm3; Z = 8. Two pseudooctahedral RuIII centers are connected by an oxo and two symmetrical acetato bridges (Ru?Ru = 3.258 (1) A?). In strongly acidic media the μ-oxo bridge is protonated (pKa = 1.9, 25°C), affording green [L2Ru2(μ-OH)(μ-CH3CO2) 2](PF6)3. The two RuIII centers are strongly intramolecularly antiferromagnetically coupled (J = -218 cm-1). Oxidation of the μ-oxo species in aqueous solution with Na2S2O8 affords the orange-brown mixed-valence species [L2RuIIIRuIV(μ-O)(μ-CH3CO 2)2](PF6)3; the crystal structure of the diperchlorate hexafluorophosphate salt has been determined by X-ray crystallography. Crystal data: monoclinic; C2/c (C2h6, No. 15); a = 35.270 (6), b = 10.661 (2), c = 21.650 (4) A?; β = 114.43 (1)°; V = 7411 A?3; ρcalcd = 1.83 g/cm3; Z = 8. The overall structure is as in the (μ-oxo)bis(μ-acetato)diruthenium(III) species; the corresponding Ru-N and Ru-O distances are shorter, but the Ru?Ru distance increases by 0.084 A?. This is in contrast to the prediction based on a simple metal-metal-bonding model, where the RuIII2 dimer has a Ru-Ru bond of order 1.0 (σ2π4π*4) that increases upon oxidation to 1.5 (σ2π4π*3). From a comparison with analogous complexes of V(III) and Fe(III), it is concluded that no metal-metal bonds exist. Electronic and 1H and 13C NMR spectra, magnetic properties, and the electrochemistry in protic and aprotic solvents of these new compounds are reported.