13/9/2021 News Extracurricular laboratory:new discovery of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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A series of cyanocarbon and cyanonitrogen derivatives 2) have been prepared from reactions between and the appropriate cyano-substituted anion.The R groups are probably attached via Ru-N bonds, i.e. they are keteniminato-comlexes; this was confirmed for R = C3(CN)5 by an X-ray diffraction study of the complex .Crystals are monoclinic, space group C2/c, a=18.845(8), b=20.967(6), c=19.336(7) Angstroem, beta=118.54(3) deg, and Z=8, the structure being refined to a residual of 0.042 for 3.646 ‘observed’ reflections.The ruthenium atom is pseudo-octahedrally co-ordinated by the cyclopentadienyl ring , the two phosphine ligands >Ru-PPh3 2.322(2), Ru-P(OMe)3 2.239(2) Angstroem>, and the ligand nirogen atom .

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

13/9/2021 News Top Picks: new discover of Dichloro(benzene)ruthenium(II) dimer

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A fast and efficient phenylselenylation of allyl acetates by diphenyl diselenide and indium(i) bromide has been achieved in neat under the catalysis of Ru(acac)3. The intermediate complex of diphenyl diselenide and indium has been isolated and identified as a polymeric pentacoordinated In(iii) selenolate complex, [In(SePh)3]n.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

13/9/2021 News Discovery of (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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We report the first practical use of SF6as a fluorinating reagent in organic synthesis. Photoredox catalysis enables the in situ conversion of SF6, an inert gas, into an active fluorinating species by using visible light. Under these conditions, deoxyfluorination of allylic alcohols is effected with high chemoselectivity and is tolerant of a wide range of functional groups. Application of the methodology in a continuous-flow setup achieves comparable yields to those obtained with a batch setup, while providing drastically increased material throughput of valuable allylic fluoride products.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Sep 2021 News Awesome and Easy Science Experiments about Dichloro(benzene)ruthenium(II) dimer

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The intermolecular dehydrogenative coupling of 1,1,1,3,5,5,5- heptamethyltrisiloxane with aromatic compounds such as aryloxazolines and arylimines in the presence of a catalytic amount of [RuCl2(p-cymene)] 2 gave the corresponding orthosilylated products in good yields.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Sep 2021 News Extended knowledge of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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New bichromophoric di- and trinuclear complexes were synthesized through coordinate strapping of one or two (bpy)2RuII/(phen)2RuII/Cp(PP h3)RuII moieties to [Zn{(MeS)8TAP}] 1, core. Thus five new complexes of the type [Zn{(MeS)8TAP}{Ru(bpy)2}][PF6] 2 2, bent and linear [Zn{(MeS)8TAP}{Ru(bpy)2}{Ru(phen)2}][PF 6]4 3 and 4, bent and linear [Zn{(MeS)8TAP}{Ru(bpy)2}{RuCp(PPh3)}][P F6]3 5 and 6, were synthesized and characterized using IR, 1H NMR, UV-visible, and mass spectral data. The trinuclear complexes 3-6 possessed bent (kappa4-S2,S3,S7,S 8)[RuII]2 and linear (kappa4-S2,S3,S12,S13 )[RuII]2 arrangements of the peripheral metallo-chromophore units. Unlike the two reversible reduction waves in complex 1 observed at E1/2 -0.34 and -0.60 V, only one reversible reduction wave was observed, between E1/2 -0.56 to -0.58 V vs. Ag/AgCl, in the di- and trinuclear complexes 2-6. Also in the anodic scans, the dinuclear complexes 2, as well as linear trinuclear complexes 4 and 6, exhibited two successive one electron oxidations, the first at E1/2 ? 0.62 V due to Ru(II)/Ru(III) process and second at E1/2 ? 1.16 V vs. Ag/AgCl due to {(MeS)8TAP}/{(MeS)8TAP}+ processes, while the bent trinuclear complexes 3 and 5 exhibited three successive one electron oxidations, i.e. one additional oxidation wave at E1/2 0.88 and 0.90 V vs. Ag/AgCl, respectively. In the fluorescence measurements, Soret excitation led to strong [Zn{(MeS)8TAP}] centered S2 emission together with a rapid intercomponent excitation energy transfer (k 107-108 s-1) to peripheral Ru(II) unit that showed emission maxima between 535 and 545 nm. Lifetime analysis showed that Ru(II)* emission predominated in the dinuclear complex 2, but its contribution dropped significantly upon formation of the trinuclear complexes, which has been explained in terms of relative variation of the LUMO energies of the linked chromophores in the excited states.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Sep 2021 News Can You Really Do Chemisty Experiments About Dichloro(benzene)ruthenium(II) dimer

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Reaction of the dimers [RuCl2(arene)]2 (arene = benzene, p-cymene, mesitylene) with bis(oxazolines) (N-N = bis(2-oxazoline) (box), 2,2-bis(2-oxazolinyl)propane (bop), 1,2-bis(2-oxazolinyl)benzene (benbox)) in the presence of NaSbF6 gives the complexes [RuCl(N-N)(arene)][SbF6] (1-8), which have been fully characterized. Treatment of these cations with AgSbF6 generates dications which in some cases are enantioselective catalysts for Diels-Alder reaction of methacrolein and cyclopentadiene. Two complexes, [RuCl(iPr-benbox)(p-cymene)][SbF6] (5) and [Ru(OH2)(iPr-bop)(mes)][SbF6]2 (10; mes = mesitylene), have been characterized by X-ray crystallography.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Sep 2021 News Some scientific research about Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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The mononuclear [Ru(bpy)2(bpym)][PF6]2 complex (bpy = 2,2?-bipyridine; bpym = 2,2?-bipyrimidine) has been prepared in its enantiopure Lambda form. Because of the chelating property of the bipyrimidine moiety, it is possible to use this chiral-at-metal complex as a chiral inorganic ligand for a second metal cation acting as a catalytic center. Here we report the synthesis and the structural characterization of a novel dinuclear Lambda-[(bpy)2Ru(bpym)RuCl(p-cymene)]3+ compound (1). The asymmetric-inducing properties of the enantiopure chiral-at-metal metalloligand have been probed during asymmetric transfer hydrogenation to ketones catalyzed by 1. This provides one of the very few illustrations of the potential of this original class of chiral inorganic ligands.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Sep 2021 News Extended knowledge of Ruthenium(III) chloride hydrate

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trans-[(dppm)2ClRu=C(CH2)3O]+ (2) (dppm=Ph2PCH2PPh2) and trans-[(dppm)2ClRu=C(CH2)2CH(CH) 3O]+ (3) cations were obtained from the reaction of cis-[RuCl2(dppm)2] (1) with 3-butyn-1-ol and 4-pentyn-2-ol, respectively. cis-Dichlororuthenim complex [RuCl2((dppene)(bpy)] (4) (dppene=Ph2PCHCHPPh2, bpy=2,2?-bipyridyl) also reacts with terminal alkynes e.g. 4-pentyn-2-ol and phenylacetylene to give cis-chloro-(oxycarbene)[(dppene)(bpy)ClRu=C(CH2)2CH (CH)3O]+ (5) and cis-chloro-(vinylidene)[(dppene)(bpy)ClRu=C=CHPh]+ (6) cations. cis-[RuCl2(bpy)2] (7) also react with 4-pentyn-2-ol to give dioxacyclic carbene dication cis-[(bpy)2Ru=(C(CH2)2CH(CH)3O) 2]2+ (8). In the reaction of RuCl2(PPh3)3 (9) with 3-butyn-1-ol the dimer [(PPh3)2ClRu=C(CH2)3O] 2 2+ (10) was obtained. The new synthesis method of 1 and cis-[RuCl2(dppm)2]·2MeOH (1a) is also presented. These complexes have been fully characterized by IR, 1H, 13C{H} and 31P{H} NMR) and single crystal X-ray diffraction for 2, 3, 5 and 1a. The catalytic activity of 10 in reactions of ROMP of norbornene was also studied.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Sep 2021 News The Absolute Best Science Experiment for Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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Ruthenium compounds of general formula Cp?RuX(PR2R?) 2 (Cp? = eta5-C5H5 (Cp), eta5-C9H7 (Ind), eta5C 5(CH3)5 (Cp*); X = Cl, CF 3C(O)O; R = C6H5 (Ph), C6H 4(CH3) (m-tolyl); R? = C6H5, C6H11 (Cy), C6H4(CH3) (m-tolyl, o-tolyl)) are examined as catalysts for the aldehyde olefination starting from diazo compounds, phosphanes, and aldehydes. Cp*RuCl(PPh 3)2 is highly active for the olefmation of several aldehydes, displaying a very high E-selectivity, as well as for ketone olefination (with benzoic acid as cocatalyst). The reaction’s mechanism is substantiated by the isolation of a catalytic active reaction species, namely, a mixed carbene/phosphane ruthenium complex, Cp*RuCl(=CHCO 2Et)(PPh3) (8). Spectroscopic studies reveal that the latter compound reacts with PPh3 to produce the phosphorus ylide Ph3P=CHCO2Et, which further reacts with the aldehyde to produce the olefin.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

10-Sep-2021 News Final Thoughts on Chemistry for Dichloro(benzene)ruthenium(II) dimer

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The mononuclear cations of the general formula [(eta6-arene)RuCl(pdpt)]+ (pdpt = 5,6-diphenyl-3-(pyridine-2-yl)-1,2,4-triazine; arene = C6H6 (1); C6H5Me (2); p-PriC6H4Me (3); C6Me6 (4)) have been synthesised from 5,6-diphenyl-3-(pyridine-2-yl)-1,2,4-triazine (pdpt) and the corresponding chloro complexes [(eta6-C6H6)Ru(mu-Cl)Cl]2, [(eta6-C6H5Me)Ru(mu-Cl)Cl]2, [(eta6p-PriC6H4Me)Ru(mu-Cl)Cl]2 and [(eta6-C6Me6)Ru(mu-Cl)Cl]2, respectively. The X-ray crystal structure analyses of [1][PF6] · (C6H6)2.5 and [2][PF6] · (CH3CN)2 reveal a typical piano-stool geometry around the metal centre and in the crystal packing a complexed networks of intermolecular interactions.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI