84206-09-7Relevant academic research and scientific papers
ELECTROCHEMISTRY OF COORDINATION COMPOUNDS. XX. ELECTROGENERATED Rh(CO)(PPh3)3 AND Ir(CO)(PPh3)3
Zotti, Gianni,Zecchin, Sandro,Pilloni, Giuseppe
, p. 61 - 72 (2007/10/02)
The redox behaviour of the d8 complexes + (M=Rh, Ir) was studied on platinum electrode in 1,2-dimethoxyethane by cyclic voltammetry, differential pulse voltammetry, and potentiostatic coulometry.The complexes show two reversible one-electron reductions consistent with the formation of the rare zerovalent M(CO)(PPh3)3 and the anionic - derivatives, respectively.The reduced species were characterized by ESR and IR spectroscopy.A significant feature is that the one-electron reduced intermediates, in spite of their radical nature, react very easily with molecules capable of reacting as proton rather than H-atom sources to give the hydride species HM(CO)(PPh3)3.A tentative interpretation of this behaviour is suggested.
PREPARATION AND REACTIVITY OF trans-Ir(CH2CN)(CO)(PPh3)2
Zecchin, Sandro,Zotti, Gianni,Pilloni, Giuseppe
, p. 353 - 368 (2007/10/02)
The preparation and characterization of the complex trans-Ir(?-CH2CN)(CO)(PPh3)2 are described.Like the isoelectronic and isostructural Vaska's complex, this iridium(I) derivative undergoes reactions with many simple molecules (CO, O2, HClO4, CH3I and H2) and is the precursor of a variety of novel iridium compounds whose stereochemistry has been assigned by IR and 1H NMR spectroscopy.Notably, the reaction with CH3I affords an unusually stable iridium(III) complex containing two metal-carbon ? bonds, while the cis-addition of hydrogen appears to follow a stereochemical pathway leading uniquely to the formation of a rare dihydrido derivative having the phosphine ligands cis to each other and trans to H.
