129096-93-1Relevant academic research and scientific papers
Electrocatalytic Reduction of CO2 to Methanol by Iron Tetradentate Phosphine Complex Through Amidation Strategy
Bi, Jiaojiao,Hou, Pengfei,Liu, Fang-Wei,Kang, Peng
, p. 2195 - 2201 (2019)
The iron complex of tetradentate tris[2-(diphenylphosphino) ethyl]phosphine (PP3), [Fe(PP3)(MeCN)2](BF4)2, was able to electrocatalytically reduce CO2 to formate with a Faradaic efficiency (FE) of approximately 97.3 % in acetonitrile. Upon addition of diethylamine as a cocatalyst, electrocatalytic reduction to methanol was achieved with an FE of 68.5 %, and other products were formamide and formate. A mechanistic study suggested that the [FeH(PP3)](BF4) hydride complex was the active species in the electrocatalysis. Added amine as cocatalyst could react with CO2 to form carbamate, which could then be reduced to formamide and further to methanol. By contrast, free CO2 could only be reduced to formate as the end-product.
A well-defined iron catalyst for the reduction of bicarbonates and carbon dioxide to formates, alkyl formates, and formamides
Federsel, Christopher,Boddien, Albert,Jackstell, Ralf,Jennerjahn, Reiko,Dyson, Paul J.,Scopelliti, Rosario,Laurenczy, Gabor,Beller, Matthias
, p. 9777 - 9780 (2011/03/16)
A will of iron: An active well-defined iron complex (see structure; gray C, white H, yellow B, green F, brown Fe, pink P) catalyzes the title reaction (see scheme). The iron-catalyzed reduction of readily available bicarbonates to formates has also been demonstrated for the first time. This reaction could be an important step in the use of CO2 for hydrogen storage. Copyright
Electrochemistry as a diagnostic tool to discriminate between classical M-(H)2 and nonclassical M-(H2) structures within a family of dihydride and dihydrogen metal complexes
Bianchini, Claudio,Laschi, Franco,Peruzzini, Maurizio,Ottaviani, Francesca M.,Vacca, Alberto,Zanello, Piero
, p. 3394 - 3402 (2008/10/08)
The redox properties of a family of dihydride and dihydrogen complexes of iron, cobalt, rhodium, and iridium have been studied in detail and compared with those of the corresponding monohydrido derivatives. All of the complexes contain as stabilizing coligands either P(CH2CH2PPh2)3 (PP3) or N(CH2CH2PPh2)3 (NP3). The novel dihydride [(PP3)Fe(H)2] and its isotopomers [(PP3)Fe(H)(D)] and [(PP3)Fe(D)2] have been fully characterized by IR and 1H and 31P NMR techniques. The complexes [(PP3)Co(H2)]PF6 and [(PP3)Rh(H2)]BF4, which exhibit the nonclassical dihydrogen structure, undergo in tetrahydrofuran irreversible one-electron oxidation. As a result, the deprotonation of the H2 ligand occurs and the starting η2-H2 compounds are converted to the corresponding monohydrides [(PP3)MH]+ (M = Co, Rh). In contrast, the classical dihydrides [(L)Ir(H)2]BPh4 (L = PP3, NP3) and [(NP3)Rh(H)2]BPh4 show no redox activity within the potential window of tetrahydrofuran. The dihydride [(PP3)Fe(H)2)] can be oxidized to give the unstable species [(PP3)Fe(H)2]+ and [(PP3)Fe(H)2]2+, but no deprotonation reaction occurs. The cis-(hydride)(dihydrogen) complex [(PP3)Fe(H)(H2)]BPh4 undergoes one-electron reduction in tetrahydrofuran to give the neutral dihydride. Rare examples of paramagnetic monohydrides of cobalt(II), rhodium(II), iron(I), and iron(II) have been synthesized chemically or electrochemically and characterized by X-band ESR spectroscopy.
