The proton spectra of all 18 possible six-carbon aliphatic alcohols have been examined with ten increasing concentrations of Eu(dpm)3 and the 13C spectra examined with four increasing concentrations of Yb(dpm)3. Utilizing the McConnell-Robertson equation, the average solution conformations of these alcohols in CS2 have been determined by both methods of spectroscopy and have been found to be the same. Experimentally, the use of Yb(dpm)3 and 13C spectroscopy has several advantages. The problem of distortion of the substrate by the shift reagent is considered in detail. The many pitfalls of this type of analysis are discussed. A linear regression analysis of the 13C chemical shifts of the 95 nonequivalent resonances in the 18 alcohols has been performed. Large correction factors in the I3C shifts are indicated for adjacent tertiary and quaternary carbons. Comparisons are made between the 13C chemical shifts of these alcohols and conformationally similar fragments of cyclohexanols. The 13C shifts of diastereotopic methyl groups are considered in detail.
Constitution and Redox Stability of Copper(II)‐Complexes with Substituted Hydrazines
CuCl2 reacts with substituted hydrazines forming chelates of the CuIIL2Cl2 type (L = RCONHNH2, RCONHN(C6H5)2, RCONHNHCOR, H2NNHCO(CH2)nCONHNH2) which are characterized by quantitative analysis, i.r. and e.p.r. spectra. The complex polyhedron exhibits the geometry of a tetragonally distorted octahedron of C2v symmetry. The complexes undergo intramolecular redox decomposition in acetonitril forming Cu(I) species.
The rate constants increase with decreasing half wave oxydation potential and decreasing Homo energy of the hydrazine ligands, respectively.
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