109905-07-9Relevant academic research and scientific papers
Reduction-Oxidation Properties of Organotransition-metal Complexes. Part 26. The Synthesis of Paramagnetic Triazenido- and Aryl(1-aryliminoethyl)amido-bridged Dirhodium Carbonyl Derivatives containing the 3+ Core
Connelly, Neil G.,Garcia, Gabriel,Gilbert, Mark,Stirling, Janet S.
, p. 1403 - 1408 (2007/10/02)
Cyclic voltammetry shows that , (3, L = PPh3 or CNBut), 2> (4, L = CO), 4-diene)2(μ-RNNNR)2> , and t)(μ-RNNNR)2> (6) undergo at least two diffusion-controlled one-electron oxidations at a platinum bead electrode in CH2Cl2.The first process is reversible for all of the complexes and corresponds to the formation of a monocation with a 3+ core.The second step is fully reversible only for (1), (3, L = PPh3), and (5, diene = nbd), and for the first two of these complexes a third reversible oxidation wave is also observed.The paramagnetic monocations (3+, L = PPh3 or CNBut), (4+, L = CO), and (5+, diene = nbd) have been isolated as stable hexafluorophosphate salts via the oxidation of the appropriate neutral complex with either or in CH2Cl2.The related complex (7+, dppm = Ph2PCH2PPh2) was also prepared, by the oxidation of a mixture of (1) and dppm.The tricarbonyl (4+, L = CO) undergoes substitution with Lewis bases, L, to give the cationic dicarbonyls +, L = PPh3, AsPh3, or P(OPh)3> which are readily reduced by n4> in CH2Cl2 to give the otherwise inaccesible neutral species .
The Synthesis of Mixed-valence Dirhodium Carbonyl Complexes, and the X-Ray Crystal Structures of 2> and 2> (R = p-Tolyl)
Connelly, Neil G.,Finn, Crispin J.,Freeman, Mark J.,Orpen, A. Guy,Stirling, Janet
, p. 1025 - 1027 (2007/10/02)
X-Ray structural studies on 2>z+ (R = p-tolyl, z = 0 and 1) show that the mixed-valence cation is formed by electron-loss from a metal-metal anti-bonding orbital; the asymmetric compounds 2>z+ result from the oxidatively induced substitution of 2>.
