Extracurricular laboratory:new discovery of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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Herein are described some continuing investigations into the reactions of cyano-alkenes with diynyl-ruthenium complexes which have resulted in the preparation and characterisation of diynyl-ruthenium compounds Ru(C?CC?CR)(PP)Cp [R = Ph, PP = dppe; R = Fc, PP = dppf; R = CPh=CBr2, PP = (PPh3)2], together with the polycyanobutadienyls Ru{C?CC[=C(CN)2]CR=CR?(CN)}(PP) Cp? [R = Fc, (PP)Cp? = (dppf)Cp; R = H, SiMe3, (PP)Cp? = (dppe)Cp*] formed by [2 + 2]-cycloaddition of the cyano-alkenes to the outer C?C triple bonds and subsequent ring-opening reactions. Single-crystal XRD molecular structure determinations of six complexes are reported. Copyright

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

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We have designed and synthesized oligosubstituted bullvalenes 1 and 2 as adaptive molecules that can change their shapes in order to bind tightly to a suitable guest. By incorporation of a photolabile o-nitroveratryloxycarbonate (NVOC) group into bullvalenes 1 and 2, tightly binding species can be selectively isolated from a population of hundreds of interconverting structural isomers. Spontaneous strain-assisted Cope rearrangements allow these shape-shifting molecules to exist in a dynamic equilibrium of configurationally distinct valence isomers, as revealed by dynamic NMR and HPLC studies. When NVOC bullvalenes 1 and 2 were exposed to UV light, the cleavage of the NVOC group resulted in a mixture of static isomers of the corresponding bullvalone. Binding studies of NVOC bisporphyrin bullvalene 1 demonstrated that the dynamic isomeric equilibrium shifted in the presence of C60, favoring configurations with more favorable binding affinities. Irradiation of a mixture of 1 and C60 with UV light and isolation of the major static isomer yielded an isomer of bisporphyrin bullvalone with a binding affinity for C 60 that was ?2 times larger than that of the nonadapted isomer bisporphyrin bullvalone 41.

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

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[Figure Presented] The wizard of Os: Regioselective osmiumcatalyzed 7-endo heterocyclization of aromatic alkynols affords benzoxepines in good yields. The proposed catalytic cycle involves the key formation of osmiumvinylidene complexes via an alkynyl-hydride-osmium(IV) complex from the starting alkynol.

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

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The 1-alkyne-1-thiolates R-CC-Sli <1: R = SiMe3, 3: (eta5-C5H4)Fe(eta5-C5H5)> react with (Ph3P)2PtCl2 and CpRu(PPh3)2Cl to give the complexes trans-(Ph3P)2Pt(S-CC-SiMe3)2 (4a).CpRu(PPh3)2S-CC-SiMe3) (4b), and cis-(Ph3P)2Pt(S-CC-eta5-C5H4)Fe(eta5-C5H5)>2 (5).The Pt(II)bis(acetylide) complex cis-(Ph3P)2Pt2 (6a) was isolated after chromatography of 5.The trans-configurated compound 6b is obtained by the reaction of Fe(eta5-C5H5) with (Ph3P)2PtCl2.The complexes are characterized by IR, 1H-, 13C-, and 31P-NMR spectroscopy, FAB mass spectrometry and X-ray diffraction (6a). – Key Words: 1-Alkyne-1-thiolato ligands / Bis(acetylide) complexes / Ferrocene derivatives / Ruthenium complexes / Platinum complexes

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

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The eta3-allylic complex 8 was obtained from thermolysis of the neutral ruthenium furyl complex 7 with an unsaturated carbon chain on the furyl ligand. Protonation of complex 8c with HBF4 generates complex 9c with an oxygen atom andan olefin group coordinated to the ruthenium metal.

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

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New ruthenium(II) and iron(II) organometallic compounds of general formula [(eta5-C5H5)M(PP)Lc][PF6], bearing carbohydrate derivative ligands (Lc), were prepared and fully characterized and the crystal structures of five of those compounds were determined by X-ray diffraction studies. Cell viability of colon cancer HCT116 cell line was determined for a total of 23 organometallic compounds and SAR’s data analysis within this library showed an interesting dependency of the cytotoxic activity on the carbohydrate moiety, linker, phosphane coligands, and metal center. More importantly, two compounds, 14Ru and 18Ru, matched oxaliplatin IC50 (0.45 muM), the standard metallodrug used in CC chemotherapeutics, and our leading compound 14Ru was shown to be significantly more cytotoxic than oxaliplatin to HCT116 cells, triggering higher levels of caspase-3 and -7 activity and apoptosis in a dose-dependent manner.

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

New explortion of Chloro(pentamethylcyclopentadienyl)bis(triphenylphosphine)ruthenium(II)

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The diazoalkane complexes [Ru(eta5-C5Me5)(N2CAr1Ar2){P(OR)3}L]BPh4 (1-4) [R = Me, L = P(OMe)3 (1); R = Et, L = P(OEt)3 (2); R = Me, L = PPh3 (3); R = Et, L = PPh3 (4); Ar1 = Ar2 = Ph (a); Ar1 = Ph, Ar2 = p-tolyl (b); Ar1Ar2 = C12H8 (c); Ar1 = Ph, Ar2 = PhC(O) (d)] and [Ru(eta5-C5Me5){N2C(C12H8)}{PPh(OEt)2}(PPh3)]BPh4 (5c) were prepared by allowing chloro-compounds RuCl(eta5-C5Me5)[P(OR)3]L to react with the diazoalkane Ar1Ar2CN2 in the presence of NaBPh4. Treatment of complexes 1-4 with H2O afforded 1,2-diazene derivatives [Ru(eta5-C5Me5)(eta2-NH=NH){P(OR)3}L]BPh4 (6-9) and ketone Ar1Ar2CO. A reaction path involving nucleophilic attack by H2O on the coordinated diazoalkane is proposed and supported by density functional theory calculations. The complexes were characterized spectroscopically (IR and 1H, 31P, 13C, 15N NMR) and by X-ray crystal structure determination of [Ru(eta5-C5Me5)(N2CC12H8){P(OEt)3}2]BPh4 (2c) and [Ru(eta5-C5Me5)(eta2-NH=NH){P(OEt)3}2]BPh4 (7).

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

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Cyclization of the ether enyne 1 catalyzed by [Ru]NCCH3+ ([Ru] = Cp(PPh3)2Ru) in CHCl3 generates a diastereomeric mixture of the substituted tetrahydropyran 11. Presumably, formation of an allenylidene complex is followed by a cyclization by nucleophilic addition of the olefinic group to C? of the ligand giving a boat-like six-membered ring. The diastereoselectivity is controlled by the 1,3-diaxial interaction. The vinylidene complex 7, a precursor of 11, is obtained from 1 and [Ru]Cl. In a mixture of MeOH/CHCl3, the domino cyclization of 1 further affords 14a, a chromene product catalytically. The second cyclization proceeds via nucleophilic addition of the resulting olefinic unit to Calpha of 7. But the ether enyne 3 with a cyclopentyl ring on the olefinic unit undergoes only single cyclization due to steric effect. The propargyl alcohol and the two terminal methyl groups on the olefinic unit shape the cyclization. Thus, similar all-carbon 1,n-enynes (n = 7, 8, 9) 4-6 each with an aromatic linker undergo direct domino cyclization catalyzed by [Ru]NCCH3+, to give derivatives of tricyclic fluorene, phenanthrene and dibenzo[7]annulene, respectively, with no intermediate observed.

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

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The mononuclear cationic complexes [(eta6-C6H6)RuCl(L)]+ (1), [(eta6-p-iPrC6H4Me)RuCl(L)]+ (2), [(eta5-C5H5)Ru(PPh3)(L)]+ (3), [(eta5-C5Me5)Ru(PPh3)(L)]+ (4), [(eta5-C5Me5)RhCl(L)]+ (5), [(eta5-C5Me5)IrCl(L)]+ (6) as well as the dinuclear dicationic complexes [{(eta6-C6H6)RuCl}2(L)]2+ (7), [{(eta6-p-iPrC6H4Me)RuCl}2(L)]2+ (8), [{(eta5-C5H5)Ru(PPh3)}2(L)]2+ (9), [{(eta5-C5Me5)Ru(PPh3)}2(L)]2+ (10), [{(eta5-C5Me5)RhCl}2(L)]2+ (11) and [{(eta5-C5Me5)IrCl}2(L)]2+ (12) have been synthesized from 4,4?-bis(2-pyridyl-4-thiazole) (L) and the corresponding complexes [(eta6-C6H6)Ru(mu-Cl)Cl]2, [(eta6-p-iPrC6H4Me)Ru(mu-Cl)Cl]2, [(eta5-C5H5)Ru(PPh3)2Cl)], [(eta5-C5Me5)Ru(PPh3)2Cl], [(eta5-C5Me5)Rh(mu-Cl)Cl]2 and [(eta5-C5Me5)Ir(mu-Cl)Cl]2, respectively. All complexes were isolated as hexafluorophosphate salts and characterized by IR, NMR, mass spectrometry and UV-vis spectroscopy. The X-ray crystal structure analyses of [3]PF6, [5]PF6, [8](PF6)2 and [12](PF6)2 reveal a typical piano-stool geometry around the metal centers with a five-membered metallo-cycle in which 4,4?-bis(2-pyridyl-4-thiazole) acts as a N,N?-chelating ligand.

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

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The reaction of [W(?CC?CSiMe3)(CO)2(Tp)] (Tp = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with [nBu4N]F and selenium in the presence of [RuCl(PPh3)2(eta-C5H5)] affords a mixture of the tricarbido complex [WRu(mu-CCC)(CO)2(PPh3)2(eta-C5H5)(Tp)] and the selenoxopropadienylidene (C3Se) complex [WRu(mu-CCCSe)(CO)2(PPh3)2(eta-C5H5)(Tp)], both of which were structurally characterized. The formation of the bimetallic C3Se complex is consistent with the intermediacy of the salt [nBu4N] [W(?CC?CSe)(CO)2(Tp)], which could be observed spectroscopically and computationally interrogated, but not yet isolated.

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