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Novel platinum group metal complexes bearing bidentate chelating pyrimidyl-NHC and pyrimidyl imidazolyl-thione ligands: Syntheses, spectral and structural characterization

A family of novel platinum group metal complexes containing bidentate chelating 1-pyrimidyl-3-methylimidazolyl bromide (HL1¡¤Br) and 1-pyrimidyl-3-methylimidazolyl-2-thione (L2) ligands has been synthesized. The synthetic protocol for the formation of these complexes differs from one ligand to the other. Treatment of ligand (HL1¡¤Br) with the metal precursors led to the formation of complexes via in situ carbene transfer reactions. The silver-NHC complex (1) was formed by the reaction of HL1¡¤Br with silver oxide under light-free conditions. Subsequent addition of appropriate metal precursors to the silver-NHC complex yielded [(eta6-arene)Ru(L1)Cl] PF6 complexes {arene = C6H6 (2), p- iPrC6H4Me (3), C6Me6 (4)} on stirring at room temperature, whereas the complexes [CpRu(L1)(PPh 3)]PF6 {Cp = C5H5 (5), C 9H7 (6)} were obtained under reflux conditions. In the case of ligand L2, stirring of equimolar quantities of metal precursors and the ligand at room temperature yielded [(eta6-arene)Ru(L2)Cl]PF 6 {arene = C6H6 (7), p-iPrC 6H4Me (8), C6Me6 (9)}, and [Cp*M(L2)Cl]PF6 {Cp* = C5Me5, M = Rh (10), Ir (11)}. All these complexes were characterized by CHN analysis, IR, NMR and mass spectrometry besides confirmation by single crystal X-ray diffraction studies for some representative complexes as their hexafluorophosphate salts [3]PF6, [5]PF6, [8]PF 6 and [10]PF6.

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

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The Syntheses and Crystal Structures of some Ten-vertex (MCB8; M=Ru or Os) Metallacarbaboranes: 9,9,9-(CO)(PPh3)2-nido-9,6-MCB8H10-5-(PPh3)> (M=Ru or Os) and <9,9,9-(eta-C5H5)(H)(PPh3)-arachno-9,6-RuCB8H12>

The reaction of M=Ru or Os) with arachno-(1-) yields the nido-metalllacarbaboranes <9,9,9-(CO)(PPh3)2-9,6-MCB8H10-5-(PPh3)> in reasonable yields as red and orange crystals respectively.A phosphine ligand is transferred from the metal atom to the cage in each case, and they both show a decarborane(14)-like cage structure with the 6- and 9-positions occupied by CH and M(CO)(PPh3)2 fragments respectively, as confirmed by single-crystal X-ray diffraction analysis.Compounds (1) and (2) are isostructural and isomorphous with their crystals are monoclinic, space group P21/n, with Z=4.R=0.087 for 2 670 observed =3.0> reflections for (1) and 0.050 for 3525 observed reflections for (2) respectively.A similar reaction with yields the arachno species <9,9,9-(eta-C5H5)(H)(PPh3)-9,6-RuCB8H12>, (3).In this case the cage arrangement as determined by a sigle-crystal X-ray diffraction study, is similar to that in (2-) with 6- and 9-positions substituted by CH2 and RuH(eta-C5H5)(PPh3) fragments, respectively.The crystals are monoclinic, space group P21/n, with Z=4, R=0.046 for 3 523 observed reflections.The application of the skeletal electron counting rules to this arachno structure is discussed.

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

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Cyclopentadienylruthenium complexes with sulphur ligands II. A comparative study of the reactivity of Ru(eta-RC5H4)Cl(L)2 (R=H, CH3, CH3CO; L=CO, Ph2PCH2CH2PPh2/2, P(CH2CH2CN)3) towards anionic (S-S) donor ligands

The complexes Ru(eta-RC5H4)Cl(PPh3)2 (R=H, CH3, CH3CO) readily react with the tertiary phosphines Ph2PCH2CH2PPh2 (dppe) and P(CH2CH2CN)3 (tcep) to give Ru(eta-RC5H4)Cl(dppe) and Ru(eta-RC5H4)Cl(tcep)2 (R=H, CH3, CH3CO).The dppe complex with R=CH3 reacts with (S2COR’)- ions to give Ru(eta-CH3C5H4)(S2COR’)(dppe) (R’=Me, Et) involving monodentate coordination of the dithiolate, and with (S2CNR’2)- ions to give Ru(S2CNR’2)2(dppe) (R’=Et).The tcep complexes do not react with the dithiolates under these conditions.The reaction of Ru(eta-C5H5)Cl(CO)2 with KS2COEt has also been studied.

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

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Reference of 32993-05-8, Chemistry can be defined as the study of matter and the changes it undergoes. You¡¯ll sometimes hear it called the central science because it is the connection between physics and all the other sciences, starting with biology.32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru. In a patent, introducing its new discovery.

Cyclopentadienyl-Ruthenium and -Osmium Chemistry. XXII. Synthesis, X-Ray Structure and Some Reactions of RuCl(PPh3)(eta1-Ph2PCH2PPh2)(eta-C5H5), Containing a Monodentate CH2(PPh2)2 Ligand

Stoichiometric amounts of RuCl(PPh3)2(eta-C5H5) and dppm react in refluxing C6H6 to give RuCl(PPh3)(eta1-dppm)(eta-C5H5), which has been fully characterized by an X-ray study (triclinic, space group P<*>, a 22.377(6), b 9.913(2), c 9.826(3) Angstroem, alpha 70.46(2), beta 78.72(2), gamma 80.40(2) deg, Z 2) in which 3299 data were refined to R 0.046, R’ 0.052.Structural parameters are similar to those of other RuX(PR3)2(eta-C5H5) complexes.The chloro complex was converted was converted into + salts; the other PPh3 ligand can be replaced by a second dppm ligand to give +, which contains both mono- and bidentate dppm ligands.Alkylation of the uncoordinated phosphorus with Mel is accompanied by halogen exchange to give I, while reactions with a variety of transition metal complexes result in abstraction of PPh3 and formation of RuCl(dppm)(eta-C5H5).

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

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A general bifunctional catalyst for the anti-Markovnikov hydration of terminal alkynes to aldehydes gives enzyme-like rate and selectivity enhancements

A new, bifunctional catalyst for anti-Markovnikov hydration of terminal alkynes to aldehydes (6) allows practical room-temperature hydration of alkyl-substituted alkynes. Other outstanding features include near-quantitative aldehyde yields from both alkyl- and aryl-substituted alkynes and wide functional group tolerance. The uncatalyzed rate of alkyne hydration is measured for the first time, showing the enzyme-like rate and selectivity enhancements of aldehyde formation by 6. For aldehyde formation, an uncatalyzed rate <1 ¡Á 10-10 mol h-1 means a half-life >600 000, years. The catalyzed rate is up to 23.8 mol (mol 6)-1 h-1 and 10 000:1 ratio in favor of aldehyde. Changes in rate and selectivity induced by 6 are thus >2.4 ¡Á 1011 and 300 000, respectively. Copyright

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

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Ruthenium-catalyzed oxidative transformations of terminal alkynes to ketenes by using tethered sulfoxides: Access to beta-lactams and cyclobutanones

The oxidation of in situ generated Ru vinylidenes to ketenes is realized with tethered sulfoxides. The result is a Ru-catalyzed oxidative transformation of terminal alkynes to highly valuable ketenes. Moreover, the ketenes generated here were shown to undergo characteristic ketene [2+2] cycloaddition reactions with tethered alkenes and external imines, yielding synthetically versatile bicyclic cyclobutanones and beta-lactams, respectively. Oxidant included: The oxidation of in situ generated Ru vinylidenes with the help of tethered sulfoxides results in the net transformation of terminal alkynes to valuable ketenes. They undergo characteristic ketene [2+2] cycloaddition reactions with tethered alkenes and external imines, yielding synthetically versatile bicyclic cyclobutanones and beta-lactams.

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

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Ruthenium metallodendrimers based on nitrile-functionalized poly(alkylidene imine)s

The preparation of the first- and second-generation of nitrile- functionalized poly(alkylidene imine) dendrimers with the organometallic ruthenium complex [Ru(eta5-C5H5) (PPh 3)2Cl] peripherally attached is described. The reaction of N,N?-bis-(cyanomethyl)piperazine (1), N,N?-bis[N?,N?- bis(cyanoethyl)aminoethyl]piperazine (2), or N,N,N?,N?- tetrakis(cyanoethyl)ethylenediamine (3) with [Ru(eta5-C 5H5)(PPh3)2Cl] (4) in the presence of TlPF6 gives the new air-stable ruthenium metallodendrimers 5, 6, and 7, respectively. These stable metallodendrimers are easily prepared and represent a novel quantitative method to solidify and chromatographically purify the otherwise semi-liquid nitrile-functionalized poly(alkylidene imine) dendrimers. The compounds were fully characterized by IR and 1H, 13C, and 31P NMR spectroscopy, and mass spectrometry. These dendrimers represent the first example of the utilization of nitrile-functionalized poly(alkylidene imine)s as cores in the preparation of metallodendrimers. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

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

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Platinum and ruthenium complexes of new long-tail derivatives of PTA (1,3,5-triaza-7-phosphaadamantane): Synthesis, characterization and antiproliferative activity on human tumoral cell lines

The alkylation of PTA, (1,3,5-triaza-7-phosphaadamantane), with long chain alkyl iodides produced the novel ionic derivatives (PTAC12H 25)I, (PTAC16H33)I and (PTAC18H 37)I. Anion exchange gave the PF6- analogs (PTAC12H25)PF6, (PTAC16H 33)PF6 and (PTAC18H37)PF 6. The new phosphines were characterized by ESI-MS, elemental analysis, 1H, 13C, and 31P NMR spectroscopy and their coordination ability was investigated towards Pt(II) and Ru(II) cores. Complexes cis-[PtCl2(PTAR)](PF6)2 (1-3) and [CpRuCl(PPh3)(PTAR)]I (5-7) have been isolated and characterized. Antiproliferative activity, given as estimated IC50, was tested for each complex against appropriate human tumoral lines (T2, SKOV3 and SW480) in comparison with cisplatin, with the parent complexes [CpRuCl(PPh 3)(PTA)] and [CpRuCl(PPh3)(PTAMe)]I and with the free ligands.

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

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Organoruthenium(ii) nucleoside conjugates as colon cytotoxic agents

Eleven ruthenium-nucleoside conjugates with the general formula [(eta5-C5H5)Ru(PP)L][PF6] (PP = 1,2-bis(diphenylphosphino)ethane (Dppe), 2PPh3, and L = 3-N-(p-cyanobenzyl)thymidine derivative ligand) are reported. Both [(eta5-C5H5)Ru(Dppe)NC-R]+ and [(eta5-C5H5)Ru(PPh3)2NC-R]+ scaffolds exhibit remarkable stability towards hydrolysis. Compounds show high cytotoxicity in HCT116 colon cancer cells, with IC50 values down to 1.0 muM. Uptake competition experiments with 2?-deoxyadenosine revealed its cellular absorption to be independent of nucleoside transporters.

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

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru. In a Article£¬once mentioned of 32993-05-8, Recommanded Product: Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

Quadratic and cubic hyperpolarizabilities of nitro-phenyl/-naphthalenyl/-anthracenyl alkynyl complexes

1-Nitronaphthalenyl-4-alkynyl and 9-nitroanthracenyl-10-alkynyl complexes [M](CC-4-C10H6-1-NO2) ([M] = trans-[RuCl(dppe)2] (6b), trans-[RuCl(dppm)2] (7b), Ru(PPh3)2(eta5-C5H5) (8b), Ni(PPh3)(eta5-C5H5) (9b), Au(PPh3) (10b)) and [M](CC-10-C14H8-9-NO2) ([M] = trans-[RuCl(dppe)2] (6c), trans-[RuCl(dppm)2] (7c), Ru(PPh3)2(eta5-C5H5) (8c), Ni(PPh3)(eta5-C5H5) (9c), Au(PPh3) (10c)) were synthesized and their identities were confirmed by single-crystal X-ray diffraction studies. Electrochemical studies and a comparison to the 1-nitrophenyl-4-alkynyl analogues [M](CC-4-C6H4-1-NO2) ([M] = trans-[RuCl(dppe)2] (6a), trans-[RuCl(dppm)2] (7a), Ru(PPh3)2(eta5-C5H5) (8a), Ni(PPh3)(eta5-C5H5) (9a), Au(PPh3) (10a)) reveal a decrease in oxidation potential for ruthenium and nickel complexes on proceeding from the phenyl- to naphthalenyl- and then anthracenyl-containing bridge. HOMO ? LUMO transitions characteristic of MCC-1-C6H4 to 4-C6H4-1-NO2 charge transfer red-shift and gain in intensity on proceeding to the ruthenium complexes; the low-energy transitions have increasing ILCT character on proceeding from the phenyl- to naphthalenyl- and then anthracenyl-containing bridge. Spectroelectrochemical studies of the Ru-containing complexes reveal the appearance of low-energy bands corresponding to chloro-to-RuIII charge transfer that red-shift on proceeding from the phenyl- to naphthalenyl- and then anthracenyl-containing bridge. Second-order nonlinear optical (NLO) studies at 1064 nm employing ns pulses and the hyper-Rayleigh scattering technique reveal an increase in quadratic optical nonlinearity upon introduction of metal to the precursor alkyne to afford alkynyl complexes and on proceeding from ligated-gold to -nickel and then to -ruthenium for a fixed alkynyl ligand. Quadratic NLO data of the gold complexes optically transparent at the second-harmonic wavelength reveal an increase in betaHRS on proceeding from the phenyl- to the naphthalenyl-containing complex. Broad spectral range third-order nonlinear optical studies employing fs pulses and the Z-scan technique reveal an increase in two-photon absorption cross-section on replacing ligated-gold by -nickel and then -ruthenium for a fixed alkynyl ligand. Computational studies undertaken using time-dependent density functional theory have been employed to assign the nature of the key optical transitions and suggest that the significant optical nonlinearities observed for the ruthenium-containing complexes correlate with the low-energy formally Ru ? NO2 band which possesses strong MLCT character, while the more moderate nonlinearities of the gold complexes correlate with a band higher in energy that is primarily ILCT in character.

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