134780-99-7

Upstream product

• 12125-72-3 (cycloheptatriene)tricarbonylchromium⁽⁰⁾ 
• 4431-24-7 1,2-bis(diphenylarsino)ethane 

Downstream Products

• 134736-60-0 mer-Cr(CO)3(η1-Ph2AsCH2CH2AsPh2)(η2-Ph2AsCH2CH2AsPh2)(1+) 
• 134736-63-3 trans-Cr(CO)2(η2-Ph2AsCH2CH2AsPh2)2(1+) 

Relevant academic research and scientific papers

Chemical and electrochemical oxidation of mer/fac-Cr(CO)3(η1-L-L)(η2-L-L) containing a pendant donor atom: ESR studies of the cations mer-[Cr(CO)3(η1-L-L)(η2-L-L)] + and trans-[Cr(CO)2(η2-L-L)2]+ (L-L = bidentate group 15 ligand)

Reactions between Cr(CO)3(C7H8) and Ph2PCH2CH2AsPh2 (ape) and Ph2AsCH2CH2AsPh2 (dae) give mer-Cr(CO)3(η1-ape)(η2-ape) and fac-Cr(CO)3(η1-dae)(η2-dae), respectively. Phosphorus-31 NMR studies show that the monodentate ape ligand is coordinated through phosphorus. Upon electrochemical oxidation in dichloromethane (0.1 M Bu4NClO4) at platinum electrodes, mer-Cr(CO)3(η1-ape)(η2-ape) is reversibly oxidized to mer-[Cr(CO)3(η1-ape)(η2-ape)] + whilst fac-Cr(CO)3(η1-dae)(η2-dae) gives fac-[Cr(CO)3(η1-dae)(η2-dae)] +, which rapidly isomerizes to mer-[Cr(CO)3(η1-dae)(η2-dae)] +. In addition, for each complex a further irreversible 1-electron process is observed at very positive potentials. ESR studies on several mer-[Cr(CO)3(η1-L-L)(η2-L-L)] + cations (L-L = bidentate group 15 ligand), electrochemically generated in a sealed tube within the ESR microwave cavity, show that they decompose very slowly to trans-[Cr-(CO)2(η2-L-L)2]+. The rate of decomposition to trans-[Cr(CO)2(η2-L-L)2]+ is faster in a nonsealed tube with nitrogen purging. The ESR spectra of the tricarbonyl and dicarbonyl 17-electron cations show both phosphorus and arsenic hyperfine structure with very similar values for the coupling constants. Chemical oxidation of mer/fac-Cr(CO)3(η1-L-L)(η2-L-L) with an equimolar (or greater) quantity of AgClO4 also gives mer-[Cr(CO)3(η1-L-L)(η2-L-L)] +. In one case, (L-L = Ph2PCH2PPh2(dpm)), when 0.5 molar equiv of AgClO4 is used, a diamagnetic intermediate silver complex is identified by phosphorus-31 NMR spectroscopy. In the presence of excess of AgClO4, the rate of decomposition of mer-[Cr(CO)3(η1-L-L)(η2-L-L)] + to trans-[Cr(CO)2(η2-L-L)2]+ is greatly enhanced, further confirming that the silver ion is a noninnocent oxidant when a pendant donor atom is present.