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A combined density functional and molecular mechanics approach (QM/MM) has been validated in a study of the substitution reactions: (i) (PH3)2Fe(CO)3 + 2ER3 mutually implies (ER3)2Fe(CO)3 + 2PH3 (ER3 = PMe3, PEt3, PMePh2, PPh3, PCyPh2, P(i)Pr3, PBz3, PCy3, AsEt3, AsPh3); and (ii) Cp’Ru(PH3)2Cl + 2ER3 mutually implies Cp’Ru(ER3)2Cl + 2PH3 (Cp’ = C5H5, C5(CH3)5; ER3 = PMe3, PEt3 P(n)Bu3, PMe2Ph, PMePh2, PPh3, AsEt3, P(OMe)3, P(OPh)3, P(OCH2)3CEt). The steric influence of the R substituents on the substitution enthalpies correlates well with experimental data. The combined QM/MM approach is also able to afford molecular structures in good accord with experimental estimates.

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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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Several dihydrogen complexes of ruthenium of the form [Cp/Cp*Ru(P-P)H2]+ (P-P = chelating diphosphine ligand) have been prepared by reaction of the corresponding neutral chloride complexes with H2 in the presence of NaB(ArF)4. Treatment with D2 or T2 gas leads to incorporation of deuterium or tritium in the dihydrogen ligand. Measurement of the resulting H-D and H-T couplings as a function of the temperature and magnetic field gives results consistent with computational studies which predict that the H-H bond distance will increase with temperature and will be significantly shortened by isotopic substitution. The degree of the observed temperature dependence is found to be a critical function of the ancillary ligand set.

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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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Cationic ruthenium dihydrogen complexes of the form [(eta-C5H5)Ru(L)(L?)(eta2-H 2)]BF4 (L = CO, L? = PCy3 (1a), PPh3 (2a), PMe2Ph (3a), PMe3 (4a) have been prepared by protonation of the corresponding neutral hydrides. Carbonyl free derivatives such as [(eta-C5H5)Ru(P P?)(eta2-H2)]BF4 (P P? = 1,2-bis(dimethylphosphino)ethane (dmpe) (5a), (1,1-dimethyl-2,2-diphenylphosphino)ethane (dmdppe) (6a), (R)-(+)-1,2-bis(diphenylphosphino)propane ((R)-prophos) (8a), bis(PPh3) (9a)) were similarly prepared. Pentamethylcyclopentadienyl analogues [(eta-C5Me5)Ru(P P?(eta2-H2)]BF4 (P P? = dmdppe (7a), (PPh3J2 (10a)) and [(eta-C5Me5)Ru(CO)(PCy3)(eta 2-H2)]BF4 (11a) have also been prepared. Identification of these species as dihydrogen complexes is based upon observation of substantial H-D coupling (22-32 Hz) in the 1H NMR spectra of the HD analogues, prepared by protonation of the corresponding deuterides. In every case studied in detail, the kinetic product of the protonation reaction is the dihydrogen complex, but an intramolecular isomerization occurs to give variable amounts of the transoid dihydride form at equilibrium. The composition of the equilibrium mixture and the rate at which the equilibrium is obtained depend upon the ligand environment. Facile rotation of the coordinated H2 ligand in the ruthenium complexes is established by the study of chiral complexes. The coordinated H2 in these complexes is substantially activated toward heterolytic cleavage. In the case of 5a, the measured pKa is 17.6 (CH3CN), with the dihydrogen form deprotonated more rapidly than the dihydride.

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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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Reactions between HC?CC?CSiMe3 and several ruthenium halide precursors have given the complexes Ru(C?CC?CSiMe 3)(L2) Cp? [Cp? = Cp, L = CO (1), PPh 3 (2); Cp? = Cp*, L2 = dppe (3)]. Proto-desilylation of 2 and 3 have given unsubstituted buta-1,3-diyn-1-y1 complexes Ru(C?CC?CH)(L2) Cp? [Cp? = Cp, L = PPh3 (5); Cp? = Cp*, L2 = dppe (6)]. Replacement of H in 5 or 6 with Au(PR3) groups was achieved in reactions with AuCl(PR3) in the presence of KN(SiMe3) 2 to give Ru(C?CC?CAu(PR3)}(L 2)Cp? [Cp? = Cp, L = PPh3, R = Ph (7); Cp? = Cp*, L2 = dppe, R = Ph (8), tol (9)]. The asymmetrically end-capped {Cp(Ph3P)2Ru} C?CC?C{Ru(dppe)Cp*} (10) was obtained from Ru(C?CC?CH)(dppe)Cp? and RuCl(PPh3)2Cp. Single-crystal X-ray structural determinations of 1-3 and 6-9 are reported, with a comparative determination of the structure of Fe(C?CC?CSiMe 3)(dppe)Cp? (4), and those of a fifth polymorph of {Ru(PPh 3)2Cp}2(muC?CC?C) (12), and {Ru(dppe)Cp}2(mu-C?CC?C) (13).

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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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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

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One for all: A group of polychlorinated marine peptides known as sintokamides show intriguing activity against hormone-refractory prostate cancer cells. Three members of the group have now been synthesized by a general strategy enabled by a ruthenium-catalyzed radical chloroalkylation of titanium enolates (see scheme). 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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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:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Reaction of the bis-bidentate ligand, 1,3-bis((3-(pyridin-2-yl)-1H-pyrazol-1-yl)methyl)benzene (NN?NN), containing two chelating pyrazolyl-pyridine units connected by an aromatic spacer with platinum group metal complexes results in a series of cationic binuclear complexes, [(eta6-arene)2Ru2(NN?NN)Cl2]2+ (arene = C6H6, 1; p-iPrC6H4Me, 2; C6Me6, 3), [(eta5-C5Me5)2M2(NN?NN)Cl2]2+ (M = Rh, 4; Ir, 5), [(eta5-C5H5)2M2(NN?NN)(PPh3)2]2+ (M = Ru, 6; Os, 7), [(eta5-C5Me5)2Ru2(NN?NN)(PPh3)2]2+ (8) and [(eta5-C9H7)2Ru2(NN?NN)(PPh3)2]2+ (9). All these complexes have been isolated as their hexafluorophosphate salts and fully characterized by use of a combination of NMR spectroscopy, IR spectroscopy and mass spectrometry. The solid state structures of three complexes, [2][PF6]2, [4][PF6]2 and [6][PF6]2, has been determined by X-ray crystallographic studies.

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

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A quite general approach for the preparation of eta5-and eta6-cyclichydrocarbon platinum group metal complexes is reported. The dinuclear arene ruthenium complexes [(eta6-arene)Ru(mu-Cl)Cl]2 (arene = C6H6, C10H14 and C6Me6) and eta5-pentamethylcyclopentadienyl rhodium and iridium complexes [(eta6-C5Me5)M(mu-Cl)Cl]2 (M = Rh, Ir) react with 2 equiv. of 4-amino-3,5-di-pyridyltriazole (dpt-NH2) in presence of NH4PF6 to afford the corresponding mononuclear complexes of the type [(eta6-arene)Ru(dpt-NH2)Cl]PF6 {arene = C10H14 (1), C6H6 (2) and C6Me6 (3)} and [(eta6-C5Me5)M(dpt-NH2)Cl]PF6 {M = Rh (4), Ir (5)}. However, the mononuclear eta5-cyclopentadienyl analogues such as [(eta5-C5H5)Ru(PPh3)2Cl], [(eta5-C5H5)Os(PPh3)2Br], [(eta5-C5Me5)Ru(PPh3)2Cl] and [(eta5-C9H7)Ru(PPh3)2Cl] complexes react in presence of 1 equiv. of dpt-NH2 and 1 equiv. of NH4PF6 in methanol yielded mononuclear complexes [(eta5-C5H5)Ru(PPh3)(dpt-NH2)]PF6 (6), [(eta5-C5H5)Os(PPh3)(dpt-NH2)]PF6 (7), [(eta5-C5Me5)Ru(PPh3)(dpt-NH2)]PF6 (8) and [(eta5-C9H7)Ru(PPh3)(dpt-NH2)]PF6 (9), respectively. These compounds have been totally characterized by IR, NMR and mass spectrometry. The molecular structures of 4 and 6 have been established by single crystal X-ray diffraction and some of the representative complexes have also been studied by UV-Vis spectroscopy.

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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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Ligand displacement reactions of the complexes of the type(Ar)Ru(PPh 3)2(CH3CN)]PF6 {Ar=Cp* (1) and indenyl (2)} have been investigated with N3-terpyridine ligands, 4?-phenyl-2,2?:6?,2? terpyridine (phterpy), 4?-(4?-pyridyl)-2,2?:6?,2? terpyridine (pyterpy) and 1,4-bis(2,2?:6,6? terpyridin-4-yl) benzene (diterpy). The complexes [(Ar)Ru(PPh3)2(CH3CN)]PF6 {Ar=Cp* (1) and indenyl (2)} are reacted with these ligands to form stable complexes of the type [Cp*Ru(PPh3)(phterpy)]BF 4 (3), [Cp*Ru(PPh3)(pyterpy)]BF4 (4), [(eta5ind)Ru(PPh3)(phterpy)]PF6 (5), [(eta5ind)Ru(PPh3)(pyterpy)]PF6 (6), [(Cp*Ru(PPh3)}2 (diterpy)](BF4) 2 (7) and [(eta5ind)Ru(PPh3)} 2(diterpy)l(PF6)2 (8) where respective ligands are coordinated in a bidentate fashion. When these reactions are carried out with chloro analogues [Cp*Ru(PPh3)2Cl] (9) and [(eta5-ind)Ru(PPh3)2Cl] (10) with respective ligands viz. phterpy and pyterpy, a mixture of products are isolated including the complex type 3-6 and [RuCl(PPh3)2(N 3-phterpy)]PF6 (11) and [RuCl(PPh3) 2(N3-pyterpy)]PF6 (12) respectively. All these complexes have been characterized by spectral and analytical data.

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