15053-59-5

Upstream product

• 70443-07-1 Rh(CNC₆H₂(CH₃)3)4⁽¹⁺⁾*ClO₄^(1-)=[Rh(CNC₆H₂(CH₃)3)4]ClO₄ 
• 22327-23-7 tris(5-chloro-1,10-phenanthroline)iron(III) 
• 70443-06-0 C₄₀H₄₄N₄Rh⁽¹⁺⁾ 

Relevant academic research and scientific papers

Cyclic Voltammetry of Rh(I) Complexes and the Oligomers. A Correlation between the Anodic Peak Potentials and the Rate Constants for the Electron Transfer Reactions with Inorganic Oxidants

The cyclic voltammogram of a CH3CN solution of + exhibits three anodic current peaks which correspond to the oxidations of the monomer, the dimer, and the trimer, with no cathodic wave on the reverse scan.The anodic peak potentials Epox in such irreversible cyclic voltammograms were determined for various Rh(I) monomers and the oligomers such as +, 2+, 2+, 2+, 3+, and 4+ (R=p-MeOC6H4 and Ph, etc; dppm=bis(diphenylphosphino)methane, dicp=1,3-diisocyanopropane).The anodic peak potentials Epox vary mainly with the degree of oligomerization of the Rh(I) complexes, decreasing in the order monomer > dimer > trimer > tetramer, in parallel with the energies of the highest occupied molecular orbitals EHOMO.It has been found that the Epox values are linearly correlated with logarithm of the rate constants for the electron transfer reactions with inorganic oxidants such as 3+ and 3+ (bpy=2,2'-bipyridine) in the context of the Marcus theory as expected when the standard oxidation potentials E0ox would be used.It is thus suggested that the anodic peak potentials of the Rh(I) complexes in the irreversible system can be used as the standard oxidation potentials as far as the relative values are concerned.

Electron Transfer from Tetrakis(isocyanide)rhodium(I) Monomers, and the Oligomers to Iron(III) and Cobalt(III) Complexes. Enhancement of the Reactivity by the Oligomerization

Electron transfer reactions from tetrakis(isocyanid)rhodium(I) (+ to iron(III) complexes of the 3+ type (N-N = 1,10-phenanthroline, 2,2'-bipyridine) proceed through precursor complexes formed between + and 3+ with 1:1, 1:2, and 2:1 stoichiometry..A similar scheme is suggested for the reaction of bis(isocyanide)bis(triphenylphosphine)rhodium(I) with the same oxidants.The intramolecular electron transfer rate constants k1 in the 1:1 precursor complexes have been determined in MeCN at 298 K.In accordance with Marcus theory, the log k1 values are linearly related with the reduction potentials of oxidants with the theoretical slope of 8.5.The + cations form oligomers in MeCN; +>n (n = 2,3), and the equilibrium constants for oligomerization have been determined.For a given oxidant 3+ (bpy = 2,2'-bipyridine), the log k1 value of +>n increases in parallel with the HOMO energy of +>n; monomer less than dimer less than trimer.