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A hybrid terpyridine-based bis(diphenylphosphino)amine ligand, terpy-C6H4N(PPh2)2: synthesis, coordination chemistry and photoluminescence studies

A new terpyridine-diphos hybrid ligand [4?-{p-(Ph2P)2NC6H4}-2,2?:6?2??-terpy] (1) and its RuII, PdII, AuI and ZnII complexes are described. Preliminary studies on absorption and emission properties are also reported.

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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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Concurrent tandem living radical polymerization: Gradient copolymers via in situ monomer transformation with alcohols

(Chemical Equation Presented) We developed concurrent tandem living radical polymerization as a novel methodology to efficiently, conveniently, and in one-pot produce gradient copolymers via in situ monomer transformation. The key is to employ a metal alkoxide [Al(Oi-Pr)3, Ti(Oi-Pr)4] and an alcohol solvent (ROH) in ruthenium-catalyzed polymerization of conventional ester-based methyl (meth)acrylate [M(M)A], where the monomer was directly transformed into R(M)A via in situ transesterification to gradually vary the monomer composition during the copolymerization. Typically, methyl methacrylate (MMA) was polymerized with a ruthenium catalyst in the presence of excess ethanol (EtOH) and Al(Oi-Pr)3 cocatalyst to give well-controlled gradient copolymers from MMA to EMA along the polymer chain, in which the original MMA was gradually converted into ethyl methacrylate (EMA) by the cocatalyst. This concurrent tandem polymerization, in conjunction with a wide variety of alcohols, efficiently and conveniently produced various gradient copolymers including long alkyl chain and PEG pendent groups. The obtained copolymers further exhibited unique physical properties different from the corresponding random and block counterparts.

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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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Structure, dynamic behavior, and catalytic activity of a novel ruthenium cyclopentadienyl complex with a tridentate P,P,O ligand

Reaction of l,2-bis(bis(o-methoxyphenyl)phosphino)ethane (o-MeO-dppe) with [RuClCp(PPh3)2] (1) at 135 C results in the formation of (eta5-cyclopentadienyl)[1-(bis(o-methoxyphenyl)phosphino-kappaP)- 2-((o-methoxyphenyl)(o-phenolato-kappaO)phosphino-kappaP)ethane]ruthenium(II ) ([RuCp(tappe)]; 3), which constitutes the first example of a ruthenium cyclopentadienyl complex with a tridentate P,P,O ligand. The X-ray structure of 3 has been determined to elucidate its solid-state structure, which shows evidence for a CH/pi interaction. An NMR study corroborates this finding, and temperature-dependent 31P and 1H NMR spectra reveal the dynamic behavior of 3 in solution. Complex 3 shows catalytic activity in the isomerization of allylic alcohols to carbonyl compounds.

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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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Synthesis, catalytic properties and biological activity of new water soluble ruthenium cyclopentadienyl PTA complexes [(C5R5)RuCl(PTA)2] (R = H, Me; PTA = 1,3,5-triaza-7-phosphaadamantane).

The new water soluble ruthenium complexes [(C5R5)RuCl(PTA)2] (R = H, Me; PTA = 1,3,5-triaza-7-phosphaadamantane) were synthesised and characterised. Their evaluation as regioselective catalysts for hydrogenation of unsaturated ketones in aqueous biphasic conditions and as cytotoxic agents towards the TS/A adenocarcinoma cell line is briefly presented.

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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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Scope and mechanistic investigations on the solvent-controlled regio- and stereoselective formation of enol esters from the ruthenium-catalyzed coupling reaction of terminal alkynes and carboxylic acids

The ruthenium-hydride complex (PCy3)2(CO)RuHCl was found to be a highly effective catalyst for the alkyne-to-carboxylic acid coupling reaction to give synthetically useful enol ester products. A strong solvent effect was observed for the ruthenium catalyst in modulating the activity and selectivity; the coupling reaction in CH2Cl2 led to the regioselective formation of gcm-enol ester products, while the stereoselective formation of (Z)-enol esters was obtained in THF. The coupling reaction was found to be strongly inhibited by PCy3. The coupling reaction of both PhCO2H/ PhC?CD and PhCO2D/ PhC?CH led to extensive deuterium incorporation on the vinyl positions of the enol ester products. An opposite Hammett value was observed when the correlation of a series of para-substituted p-X-C6H 4CO2H (X = OMe, CH3, H, CF3, CN) with phenylacetylene was examined in CDCl3(rho = +0.30) and THF(rho = -0.68). Catalytically relevant Ru-carboxylate and -vinylidenecarboxylate complexes, (PCy3)2(CO)(Cl) Ru(kappa2-O2CC6H4-p-OMe) and (PCy3)2(CO)(Cl)RuC(=CHPh)O2CC6H 4-p-OMe, were isolated, and the structure of both complexes was completely established by X-ray crystallography. A detailed mechanism of the coupling reaction involving a rate-limiting C-O bond formation step was proposed on the basis of these kinetic and structural studies. The regioselective formation of the gem-enol ester products in CH2Cl2 was rationalized by a direct migratory insertion of the terminal alkyne via a Ru-carboxylate species, whereas the stereoselective formation of (Z)-enol ester products in THF was explained by invoking a Ru-vinylidene species.

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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-catalyzed intramolecular amination reactions of aryl-and vinylazides

The catalytic activity of a series of ruthenium complexes for C-H amination reactions of organic azides was investigated. The most active catalyst was found to be RuCl3, which promotes C-H amination reactions of ortho-aryl phenylazides, l-azido-2-arylvinylazides, and 1-azido-1,3-butadienes to give carbazoles, indoles, and pyrroles, respectively. Both computational and experimental results support that a two-step process involving formal electrocyclization is involved in the catalytic reaction.

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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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Dimerisation and reactivity of HCCCCFc at ruthenium centres

In contrast to the simple diynyl complexes formed in reactions between HCCCCFc and MCl(dppe)Cp; (M = Fe, Ru), an analogous reaction with RuCl(PPh 3)2Cp; in the presence of KPF6 and dbu resulted in dimerisation of the diyne at the Ru centre to afford a mixture of [Ru{eta1,eta2-C(CCFc)C(L)CHCCCHFc}(PPh 3)Cp]PF6 (L = dbu 1, PPh3 2). Similar reactions with RuCl(PR3)2L gave [Ru{eta1, eta2-C(CCFc)C(dbu)CHCCCHFc}(PR3)L]PF6 (L = Cp, R = Ph 3, m-tol 4; L = eta5-C9H7, R = Ph 5). The reaction between 3 and I2, followed by crystallization of the paramagnetic product from MeOH, afforded the dicationic [Ru{C(CCFc)C(dbu) CHC(OMe)C(OMe)CHFc}(PPh3)Cp](I3)2 6. The molecular structures of 2¡¤2CH2Cl2 and 6.S (S = 2CH2Cl2, C6H6) were determined by single-crystal XRD studies.

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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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Trichlorostannyl complexes of Ruthenium(II): Synthesis, structure, reactivity and computational studies

Trichlorostannyl complexes [Ru(SnCl3) (Cp?)L] (2a-c) were prepared by treatment of optically active half-sandwich chlorocomplexes [RuCl(Cp?)L] (1a-c) with an excess of SnCl2.2H2O in ethanol. Treatment of trichlorostannyl complexes 2a-c with NaBH4 afforded trihydridostannyl derivatives [Ru(SnH3) (Cp?)L] (3a-c) in moderated yields. Treatment of 2a-c with MgBrMe gave the trimethylstannyl complexes Ru(SnMe3) (Cp?)L (4a-c). Alkynylstannyl derivatives [Ru{Sn(C?CPh)3}(Cp?)L] (5a-c) were prepared by treatment of trichlorostannyl compounds 2a-c with an excess of LiC?CPh in thf. All the complexes present optical activity. The complexes were characterized spectroscopically and by X-ray crystal structure determination of [RuCl(eta5-C5Me5)L] (1b), [Ru(SnCl3) (eta5-C5Me5)L] (2b), and [Ru(SnCl3) (eta5-C9H7)L] (2c). The influence of different ligands on the Ru?P interaction in several complexes 1a-c, 2a-c and 3a-c was evaluated by DFT calculations. These calculations indicate that [SnCl3]- has a stronger stabilization effect than [Cl]- and the same occurs between ?C9H7 and ?C5Me5. These relative stabilities combined with the distortion energies of the fragments produce a stabilizing effect in the Ru?P bonds of complex 2c that is twice as strong as in the 1b complex.

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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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Synthesis, protonation, and reduction of ruthenium-peroxo complexes with pendent nitrogen bases

Cyclopentadienyl and pentamethylcyclopentadienyl ruthenium(II) complexes have been synthesized with cyclic (RPCH2NRCH2)2 ligands, with the goal of using these [CpRRu(PR 2NR2)]+ complexes for catalytic O2 reduction to H2O (R = t-butyl, phenyl; R = benzyl, phenyl; R? = methyl, H). In each compound, the Ru is coordinated to the two phosphines, positioning the amines of the ligand in the second coordination sphere where they may act as proton relays to a bound dioxygen ligand. The phosphine, amine, and cyclopentadienyl substituents have been systematically varied in order to understand the effects of each of these parameters on the properties of the complexes. These CpR?Ru(PR 2NR2)+ complexes react with O 2 to form eta2-peroxo complexes, which have been characterized by NMR, IR, and X-ray crystallography. The peak reduction potentials of the O2 ligated complexes have been shown by cyclic voltammetry to vary as much as 0.1 V upon varying the phosphine and amine. In the presence of acid, protonation of these complexes occurs at the pendent amine, forming a hydrogen bond between the protonated amine and the bound O 2. The ruthenium-peroxo complexes decompose upon reduction, precluding catalytic O2 reduction. The irreversible reduction potentials of the protonated O2 complexes depend on the basicity of the pendent amine, giving insight into the role of the proton relay in facilitating reduction.

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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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Synthesis and reactivity of trihydridostannyl complexes of ruthenium and osmium

Trichlorostannyl complexes M(SnCl3)(Tp)L(PPh3) (1, 2) and M(SnCl3)(Cp)L(PPh3) (5, 6) [M = Ru, Os; L = P(OMe)3 (a), P(OEt)3 (b), PPh(OEt)2 (c), PPh3 (d)] were prepared by allowing chloro complexes MCl(Tp)L(PPh3) and MCl(Cp)L(PPh3) to react with an excess of SnCl2 ¡¤ 2H2O in ethanol. Treatment of trichlorostannyl complexes 1, 2, 5, and 6 with NaBH4 in ethanol yielded tin trihydride derivatives M(SnH3)(Tp)L(PPh3) (3, 4) and M(SnH3)(Cp)L(PPh3) (7, 8). Reaction of these complexes with CCl4 gave the trichlorostannyl precursors 1, 2, 5, and 6. Hydridochlorostannyl intermediates Os(SnH2Cl)(Tp)[P(OMe) 3](PPh3) (9a) and Os(SnHCl2)(Tp)[P(OMe) 3](PPh3) (10a) were also obtained. Reaction of trihydridostannyl complexes M(SnH3)(Tp)L(PPh3) (3, 4) with CO2 (1 atm) led to hydridobis(formate) derivatives M[SnH(OC(H)=O]2](Tp)L(PPh3) (11). In contrast, reaction of the related complexes M(SnH3)(Cp)L(PPh3) (7, 8) with CO2 (1 atm) led to the binuclear OH-bridging bis(formate) derivatives [M[Sn{OC(H)=O)2(mu-OH)](Cp)L(PPh3)]2 (12, 13). A reaction path for the formation of 12 and 13, involving the mononuclear tin hydride complex M[SnH(OC(H)=O]2](Cp)L(PPh3), is discussed. The X-ray crystal structure of 12b is reported. Chlorobis(methyl) stannyl Ru(SnClMe2)(Cp)[P(OEt)3](PPh3) (15b) and trimethylstannyl complexes M(SnMe3)(Tp)[P(OMe) 3](PPh3) (14a) and M(SnMe3)(Cp)[P(OEt) 3](PPh3) (16b, 17b) were prepared by allowing trichlorostannyl compounds 1, 2, 5, and 6 to react with MgBrMe in diethyl ether. Trialkynylstannyl derivatives M[Sn(C?CR)3)(Tp)L(PPh 3) (18, 19) and Ru[Sn(C=CR)3)(Cp)[P(OEt) 3](PPh3) (20b) (R = Ph, p-tolyl) were also prepared from the reaction of trichlorostannyl complexes 1, 2, 5, and 6 with Li +(C=CR)- in thf. The complexes were characterized by spectroscopy and by X-ray crystal structure determination of Ru(SnClMe 2)(Cp)[P(OEt)3](PPh3)(15b).

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