Volumetric properties and electrolytic conductances of aqueous ternary mixtures of hydrogen chloride and some transition metal chlorides at 25°C

Densities and electrolytic conductances of hydrochloric acid and ternary aqueous solutions of HCl with manganese(II), copper(II), and cadmium(II) chlorides, respectively, have been measured from about 0.2 m to ternary saturation points at several constant molalities of the salt, MnCl₂, or that of HCl for the system MnCl₂–HCl–H₂O as well as at constant total molal ionic strength of I=10.0 for all the three ternary systems (Mn, Cu, Cd)Cl₂–HCl–H₂O at 25°C. The molality dependence of the calculated volume of mixing changes V _m and of the specific conductances are discussed on the basis of the different degrees of complex formation of the bivalent transition metal chlorides in the presence of excess amounts of chloride anions in the form of HCl. It was to be seen from the present results that even the manganese(II) chloride, which behaves as a fairly strong electrolyte in dilute aqueous solutions, is considerably complexed at high concentrations of HCl, with the degree of complexation of the cations increasing in the sequence Mn^2–2–2–.Part of this publication was presented at the XIX International Conference on Solution Chemistry (XIX ICSC), Lund, Sweden, August 15–18, 1988.     

On the Kinetics of Manganese Ferrite Formation From Aqueous Solution of MnO2 and FeSO4⋅7H2O

The authors present the results of a kinetic investigation concerning the formation and growth of the primary particles of the ferrite phase in isothermal conditions, in static and well-stirred regimes. The kinetics of coprecipitation is described with the help of equations corresponding to the homogeneous nucleation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Reaction of dicymantrenylketone with mesitylmagnesium bromide

The reaction of dicymantrenyl ketone with the Grignard reagent 2,4,6-Me₃C₆H₂MgBr in THF occurs as the insertion of the mesityl substituent in the -position of one of the cyclopentadienyl rings to give (2-mesitylcymantrenyl) cymantrenyl ketone (4), rather than as addition at the C=O group. Reduction of4 by NaBH₄ in a THF-EtOH mixture affords (2-mesitylcymantrenyl)cymantrenylmethanol (5). Ionic hydrogenation of5 with the HSiEt₃/CF₃COOH system gives (2-mesitylcymantrenyl)cymantrenylmethane (7). The structure of alcohol5 has been established by X-ray diffraction analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 723–728, April, 1994.     

On the inductive effects of the organometallic groups M(CO) m Cp n and HgM(CO) m Cp n (M = Co,Mo, Mn,Fe, Re)

Based on the dependences v(CO) =a + b^* for IR spectra of carbonyi complexes of transition metals, the inductive constants of the organometallic fragments M(CO) _m Cp _n and HgM(CO) _m Cp _n (M = Co, Mo, Mn, Fe, Re) have been determined. The acceptor properties of the organometallic fragments have been shown to change according to the order of the nucleophilicity of the anions: Fe(CO)₂Cp > Re(CO)₅ > Mn(CO)₅ > Mo(CO)₃Cp > Co(CO)₄.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1482–1484, August, 1994.     

Acetylation and benzoylation of η5,η5-fulvalenedimanganesehexacarbonyl

⁵,⁵-Fulvalenedimanganesehexacarbonyl (dicymantrenyl) was acetylated and benzoylated by RC(O)Cl+AlCl₃ in CH₂Cl₂, under conditions of the Friedel-Crafts reaction. The reaction involves both nonequivalent positions of the cyclopentadienyl rings to give mixtures of two isomeric ketones. When using an excess of the acetylating mixture, diacetyl derivatives of dicymantrenyl were obtained.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2017–2020, October, 1995.The authors are grateful to P. V. Petrovsky and E. V. Vorontsov (the NMR laboratory of the Institute of Organoelement Compounds, Russian Academy of Sciences) for recording¹H NMR spectra.     

Mn(OAc)3—an efficient oxidant for regeneration of DDQ: deprotection of p-methoxy benzyl ethers

Mn(OAc)₃ has been successfully developed as a new oxidant for the regeneration of DDQ from HDDQ. This DDQ regeneration technique, making use of 3 equiv. of Mn(OAc)₃–DDQ (10 mol%), was applied to the deprotection of p-methoxy benzyl (PMB) ethers.     

Pillared salicylaldehyde derivatives as building blocks for the design of cofacial salen-type ligands

The syntheses of pillared salicylaldehyde derivatives on a naphthalene block are reported. These compounds can be considered as building blocks for the elaboration of cofacial salen-typed ligands. The X-ray structure of a dinuclear manganese(III) complex is described, supporting our strategy to build topologically controlled multinuclear metal complexes.     

Mn2(CO)10‐induced controlled/living radical copolymerization of vinyl acetate and methyl acrylate: Spontaneous formation of block copolymers consisting of gradient and homopolymer segments

The controlled/living radical polymerization of vinyl acetate (VAc) and its copolymerization with methyl acrylate (MA) were investigated in bulk or fluoroalcohols using manganese complex [Mn₂(CO)₁₀] in conjunction with an alkyl iodide (R? I) as an initiator under weak visible light. The manganese complex induced the controlled/living radical polymerization of VAc even in the fluoroalcohols without any loss of activity. The R? I/Mn₂(CO)₁₀ system was also effective for the copolymerization of MA and VAc, in which MA was consumed faster than VAc, and then the remaining VAc was continuously and quantitatively consumed after the complete consumption of MA. The ¹H and ¹³C NMR analyses revealed that the obtained products are block copolymers consisting of gradient MA/VAc segments, in which the VAc content gradually increases, and homopoly(VAc). The use of fluoroalcohols as solvents increased the copolymerization rate, controllability of the molecular weights, and copolymerizability of VAc. The saponification of the VAc units in poly(MA‐grad‐VAc)‐block‐poly(VAc) resulted in the corresponding poly(MA‐co‐γ‐lactone)‐block‐poly(vinyl alcohol) due to the intramolecular cyclization between the hydroxyl and neighboring carboxyl groups in the gradient segments. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1343–1353, 2009