52490-94-5

Usage

Reactions

Ruthenium catalyst used for the hydrogenation of carbon dioxide. Ruthenium catalyst used for a selective monoarylation reaction in water.

Upstream product

• 154986-82-0 RuCl2(η(6)-p-cymene)(4-cyanopyridine) 
• 603-35-0 triphenylphosphine 
• 88496-72-4 RuCl2(1,4-bis(diphenylphosphino)butane)(PPh3) 
• 52462-29-0 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 
• 67-64-1 acetone 
• 15529-49-4 tris(triphenylphosphine)ruthenium(II) chloride 
• 7647-01-0 hydrogenchloride 
• 948302-04-3 Ru(H)(Cl)(PPh3)(η6-p-cymene) 
• 1346137-06-1 [RuCl₂(p-cymene)-(SOC*SIMes)] 
• 846550-68-3 [chlororuthenium(II) bis(triphenylphosphane)(η6-p-cymene)] hexafluorophosphate 
• 75-09-2 dichloromethane 
• 100928-22-1 (p-cymene)ruthenium(II) chloride 
• 7647-14-5 sodium chloride 

Downstream Products

• 302911-45-1 [Ru(η6-C10H14)(PPh3)Cl((CN)2C6H4)]PF6 
• 302911-31-5 [Ru(η6-C10H14)(PPh3)Cl(CNC5H4N)]PF6 
• 846550-68-3 [chlororuthenium(II) bis(triphenylphosphane)(η6-p-cymene)] hexafluorophosphate 
• 362632-52-8 [(η6-p-cymene)RuCl(PPh3)(imidazole)]BF4 
• 210570-09-5 [(CH₃C₆H₄CH(CH₃)2)RuCl(C₃(C₆H₅)2)(P(C₆H₅)3)]⁽¹⁺⁾*PF₆^(1-)=[(CH₃C₆H₄CH(CH₃)2)RuCl(C₃(C₆H₅)2)(P(C₆H₅)3)](PF₆) 
• 163625-50-1 (CH₃C₆H₄CH(CH₃)2)Ru(Br)(C₆H₅)(P(C₆H₅)3) 
• 592534-25-3 (η6-4-methylisopropylbenzene)(PPh3)Ru(P(2,4,6-tri-tert-butylphenyl)) 
• 190195-14-3 [(η(6).-cymene)RuI2(triphenylphosphine)] 
• 819800-20-9 [(η(6).-cymene)RuCl(quinoline)(triphenylphosphine)]PF6 
• 827344-43-4 [(η(6)-p-cymene)Ru(PPh3)(p-chloroaniline)Cl]BF4 
• 912672-30-1 [(2,6-dimesitylphenyl)(2,6-diethylphenyl)Ge(μ-S)2Ru(η6-p-cymene)] 
• 912672-40-3 (germanium)(2,6-diethylphenyl)(2,6-dimesitylphenyl)bis-(μ-S)(ruthenium)(PPh3) 
• 499215-01-9 [(η6-p-cymene)ruthenium(II)Cl(triphenylphosphine)(CHCPh(PPh3)](PF6) (diethyl ether) 
• 945971-57-3 [(η6-p-cymene)ruthenium(II)Cl(triphenylphosphine)(CHC(p-tolyl)Ph(PPh3)](PF6) 

Relevant academic research and scientific papers

Labile coordination approach for the modulation of the electronic properties of ruthenium(II) and iridium(III) complexes within an n-heterocyclic carbene (NHC)-pyridyl dynamic platform

Modulating the functionality of a synthetic transition metal complex by external stimuli is highly important for designing switchable systems. One prerequisite for achieving such dynamic activity is to generate molecular systems with in situ controllable electronic properties. To achieve dynamic control of the electronic properties, here we report the synthesis of two new N-heterocyclic carbene (NHC)-pyridyl IrIII/IrIII (3) and RuII/RuII (4) bimetallic complexes. These complexes include a latent stimuli-responsive labile site. This is utilized successfully for the on-demand, real-time modulation of the electronic properties of the systems in a reversible manner using external agents, as probed by spectroscopic and electrochemical techniques. These results display promising scope in the domain of transition metal-NHC chemistry, which can guide us in developing future smart organometallic systems. the Partner Organisations 2014.

Synthesis, characterization and behavior in water/DMSO solution of Ru(II) arene complexes with bioactive carboxylates

The reactions of [RuCl(μ-Cl)(η6-p-cymene)]2 with sodium carboxylates, in methanol or acetonitrile solution, afforded the complexes [RuCl(κ2O-RCO2)(η6-p-cymene)] (RCO2 = valproate, 1; aspirinate, 2; diclofenate, 3), in 79–96% yields. Analogously, [RuCl(κ2O-dfCO2)(η6-benzene)], 4, was obtained in admixture with minor by-products from [RuCl(μ-Cl)(η6-benzene)]2 and sodium/silver diclofenate. The sequential reaction of [RuCl(μ-Cl)(η6-p-cymene)]2 with sodium salicylate and PPh3 gave [Ru(κ2O,O′-salCO2)(PPh3)(η6-p-cymene)], 5, in 70% yield. The hydride complex [Ru2Cl2(μ-Cl)(μ-H)(η6-p-cymene)2], 6, was produced in 36% yield from [RuCl(μ-Cl)(η6-p-cymene)]2 and sodium formate. An optimization of the experimental work-up allowed to isolate [RuCl(μ-Cl)(η6-p-cymene)]2 with an improved yield respect to the literature (98% vs. 65%). The bidentate coordination mode of the carboxylato ligands in 1–5 was unambiguously ascertained by IR and NMR spectroscopy, moreover the solid state structure of 1 was elucidated by single crystal X-ray diffraction. Complexes 1–3 experience rapid and quantitative dissociation of the carboxylato anion in DMSO/water/NaCl mixtures, mainly converting into [RuCl2(DMSO)(η6-p-cymene)], 7.

Ruthenium-catalysed multicomponent synthesis of borasiloxanes

We present the selective atom economical synthesis of borasiloxanes using a multi-component approach directly by the one-pot ruthenium catalysed reaction of boranes, silanes and water.

Somatostatin subtype-2 receptor-targeted metal-based anticancer complexes

Conjugates of a dicarba analogue of octreotide, a potent somatostatin agonist whose receptors are overexpressed on tumor cells, with [PtCl 2(dap)] (dap = 1-(carboxylic acid)-1,2-diaminoethane) (3), [(η6-bip)Os(4-CO2-pico)Cl] (bip = biphenyl, pico = picolinate) (4), [(η6-p-cym)RuCl(dap)]+ (p-cym = p-cymene) (5), and [(η6-p-cym)RuCl(imidazole-CO 2H)(PPh3)]+ (6), were synthesized by using a solid-phase approach. Conjugates 3-5 readily underwent hydrolysis and DNA binding, whereas conjugate 6 was inert to ligand substitution. NMR spectroscopy and molecular dynamics calculations showed that conjugate formation does not perturb the overall peptide structure. Only 6 exhibited antiproliferative activity in human tumor cells (IC50 = 63 ± 2 μ in MCF-7 cells and IC50 = 26 ± 3 μ in DU-145 cells) with active participation of somatostatin receptors in cellular uptake. Similar cytotoxic activity was found in a normal cell line (IC50 = 45 ± 2.6 μ in CHO cells), which can be attributed to a similar level of expression of somatostatin subtype-2 receptor. These studies provide new insights into the effect of receptor-binding peptide conjugation on the activity of metal-based anticancer drugs, and demonstrate the potential of such hybrid compounds to target tumor cells specifically.

Synthesis and catalytic evaluation of ruthenium-arene complexes bearing imidazol(in)ium-2-thiocarboxylate ligands

Five new complexes with the generic formula [RuCl2(p-cymene) (SOC·NHC)] (2-6) were isolated in high yields by reacting the [RuCl 2(p-cymene)]2 dimer with a range of imidazol(in)ium-2- thiocarboxylate zwitterions bearing cyclohexyl, 2,4,6-trimethylphenyl (mesityl), or 2,6-diisopropylphenyl groups on their nitrogen atoms in CH 2Cl2 at -20 °C. All the products were fully characterized by IR and NMR spectroscopy, and the molecular structures of [RuCl2(p-cymene)(SOC·IMes)] (3) and [RuCl2(p- cymene)(SOC·SIMes)] (5) were determined by X-ray diffraction analysis. Coordination of the NHC·COS ligands took place via the sulfur atom. A remarkable shielding of the methine proton on the p-cymene isopropyl group was observed by 1H NMR spectroscopy for complexes 3-6. It is most likely caused by the aromatic ring current of a neighboring mesityl or 2,6-diisopropylphenyl substituent. The catalytic activity of compounds 2-6 was probed in the ring-opening metathesis polymerization (ROMP) of cyclooctene, in the atom transfer radical polymerization (ATRP) of methyl methacrylate, and in the synthesis of enol esters from 1-hexyne and 4-acetoxybenzoic acid. In all these reactions, the [RuCl2(p-cymene)(SOC·NHC)] complexes displayed performances slightly inferior to those exhibited by [RuCl 2(p-cymene)(NHC)] species that result from the reaction of [RuCl 2(p-cymene)]2 with NHC·CO2 inner salts. However, they were significantly better catalyst precursors than the much more robust chelates of the [RuCl(p-cymene)(S2C·NHC)]PF6 type obtained by coordination of NHC·CS2 betaines to the ruthenium dimer. These results suggest that the Ru-(SOC·NHC) motif undergoes a dethiocarboxylation under the experimental conditions adopted for the catalytic tests and leads to the same elusive Ru-NHC active species as the preformed [RuCl2(p-cymene)(NHC)] family of complexes.

Catalytic activity of bis-phosphine ruthenium(II) - Arene compounds: Chemoselective hydrogenation and mechanistic insights

Bis-phosphine ruthenium(II)-arene complexes have been found to be highly active and chemoselective catalysts for the hydrogenation of aldehydes in the presence of olefinic bonds. Mechanistic studies, including comparisons with a structural analogue, reactions of an isolated hydride complex, base poisoning experiments, and a computational analysis, help rationalize the preferential hydrogenation of C=O bonds, which is suggested to proceed via an ionic outer-sphere mechanism.

Half-sandwich chloro complexes as ligands for RuCl2L2 (L = PR3, alkene): Syntheses, structures, and catalytic activity of new homo- and heterobimetallic complexes

Homo- and heterobimetallic complexes, in which half-sandwich complexes of ruthenium(II), rhodium(III), and iridium(III) are connected via three chloro bridges to RuCl2(PPh3)2, have been synthesized. The complexes were obtained in quantitative yields by reaction of [(cymene)RuCl(μ-Cl)]2 or [Cp*MCl(μ-Cl)]2 (M = Rh, Ir) with [(PPh3)2ClRu(μ-Cl)3Ru(Me2CO) (PPh3)2] (2). The crystal structure of 2 has been determined by X-ray analysis. Evidence that half-sandwich chloro complexes are generally suited for stabilizing RuCl2L2 fragments is provided by the synthesis of complexes [(cymene)Ru(μ-Cl)3RuCl(dppb)] [dppb = 1,4-bis(diphenylphosphanyl)butane] and [(cymene)Ru(μ-Cl)3RuCl(cod)] (cod = 1,5-cyclooctadiene), both of which have been structurally characterized. The abilities of all the complexes to catalyze the oxidation of secondary alcohols with 2-butanone have been investigated. The complex [Cp*Rh(μ-Cl)3RuCl(PPh3)2] has proved to be highly active, displaying a performance superior to that of previously known catalysts such as [RuCl2(PPh3)3]. Using a substrate/catalyst ratio of 500:1, initial turnover frequencies of up to 3400 h-1 were observed. The potential of these types of bimetallic complexes to act as catalysts for other reactions is discussed.

Synthesis, characterization, reactivity and structure of some mono and binuclear (η6-p-cymene)ruthenium(II) complexes

Reactions of [{Ru(η6-C10H14)Cl2}2] (η6-C10H14=p-cymene H3C-C6H4-CH(CH3)2) with 4-cyanopyridine (referred hereafler as CNPy) in 1:1 and 1:2 molar ratios in dichloromethane yields the binuclear complex [{Ru(η6-C10H14)Cl2} 2(μ-CNPy)] and the mononuclear complex [Ru(η6-C10H14)Cl2(CNPy)]. The latter complex further reacts with [{Ru(η6-C6Me6)Cl2}2] and [Ru(η5-C5H5)(PPh3) 2Cl] to give 4-cyanopyridine bridged complexes [Cl2(η6-C10H 14)Ru(μ-CNPy)Ru(μ6-C6Me 6)Cl2] and [Cl2(η6-C10H 14)Ru(μ-CNPy)Ru(η5-C5H 5)(PPh3)2]+. The complex [Ru(η6-C10H14)Cl2(CNPy)] also undergoes metathetical reactions with EPh3 (E=P, As or Sb) to give complexes with the general formulations [Ru(η6-C10H14)Cl2(EPh 3)], however its reaction with diphenylphosphinomethane (dppm) in a 1:1 ratio gives the mononuclear complex [Ru(η6-C10H14)Cl2(dppm)] in which the dppm ligand is present in uncommon coordination mode (η1-dppm). The reaction products have been characterized by microanalyses and spectroscopic studies (IR, 1H-, 13C-, 31P-NMR). The structure of [Ru(η6-C10H14)Cl2(CNPy)] [a=10.984(1), b=14.052(1), c=12.189(1) A; β=114.810(1)°; V=1707.8(4) A3; Dcalc=1.596 g cm-3; monoclinic P21/c; Z=4] and confirmation of uncommon coordination mode of dppm, in [Ru(η6-C10H14)Cl2(dppm)] [a=11.504(3), b=19.532(3), c=15.942(3) A; β=96.08(2)°; V=3562(2) A3; Dcalc=1.446 g cm-3; monoclinic P21/n; Z=4] has been determined by X-ray crystallography.