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Synthesis, characterization and electrochemistry of cyclopentadienyl phosphine nitrosyl cyanide complexes of ruthenium(II) and osmium(II). Preparation of the dicyano ruthenium(II) complex, <(eta5-C5H5)Ru(PPh3)(CN)2>Na

A series of novel chiral metal centre complexes of the general form, <"cp"M(PPh3)(NO)(CN)>PF6 with “cp” = eta5-C5H5, M = Ru (1); “cp” = eta5-C5H4-Me, M = Ru (2); “cp” = eta5-C5Me5, M = Ru (3) and “cp” = eta5-C5H5, M = Os (4), has been synthesized in 85percent yield from the corresponding bis-phosphine complexes, <"cp"M(PPh3)2CN>, and characterized by NMR (1H; 31P; 13C) and FTIR spectroscopies.Cyclic voltammetry of 1-4 indicates quasi-reversible MI/II redox couples at potentials (vs.KCl(aq) SCE) of E1/2 -0.125, -0.155, -0.30 and -0.315 V, respectively.Near quantitative syntheses of the precursor bis-phosphine cyanide complexes, from the bis-phosphine halides, have been achieved by using methanolic sodium cyanide.The complex <(eta5-C5H5)Ru(PPh3)(CN)2>Na (6) has been synthesized by treating 1 with sodium azide in acetonitrile followed by methanolic sodium cyanide.

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

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Valence tautomerism in titanium enolates: Catalytic radical haloalkylation and application in the total synthesis of neodysidenin

(Chemical Equation Presented) A direct ruthenium-catalyzed radical chloroalkylation of N-acyl oxazolidinones capitalizing on valence tautomerism of titanium enolates has been developed. The chloroalkylation method served as the centerpiece in the enantioselective total synthesis of trichloroleucine-derived marine natural product neodysidenin.

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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 Heck-Type Alkenylation of Alkyl Bromides

The complex [CpRuCl(PPh3)2] displays a high catalytic activity for the Heck-type alkenylation of alkyl bromides in the first example using this metal under thermal conditions. The coupling reaction proceeds efficiently with a variety of functionalized tertiary, secondary, and primary alkyl bromides. The presence of Huenig’s base has been revealed to be crucial for this transformation. Preliminary mechanistic studies support the participation of alkyl radicals in the reaction.

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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 piano-stool complexes containing mono- or bidentate pyrrolidinylalkylphosphines and their reactions with small molecules

Ruthenium piano-stool complexes incorporating the new bidentate aminoalkylphosphine ligand 1,2-bis(dipyrrolidin-1-ylphosphino)ethane (dpyrpe, I) or its monodentate counterpart bis(pyrrolidin-1-yl)methylphosphine (pyr 2PMe, II) have been prepared, [(C5R5)RuCl(PP)] (R = Me and PP = dpyrpe, 1; R = Me and PP = (pyr2PMe)2, 2; R = H and PP = dpyrpe, 3). Complexes 2 and 3 have been characterized by X-ray crystallography. Complexes 1 and 2 react with NaBAr4f in the presence of ligand L to yield [Cp*Ru(L)(dpyrpe-kappa2P)] [BArf4] (L = MeCN, 4a; CO, 4b; N2, 4c) and [Cp*Ru(L)(pyr2PMe)2][BAr4f] (L = MeCN, 5a; CO, 5b; N2, 5c). Complex 4a was crystallographically characterized. The CO complexes 4b and 5b were examined using IR spectroscopy in an attempt to establish the electron-donating capabilities of I and II. Complex 1 oxidatively adds H2 in the presence of NaBAr4 f to yield the Ru(IV) dihydride [Cp*RuH2(dpyrpe- kappa2P)][BAr4f], 7.

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