66289-72-3Relevant academic research and scientific papers
Conversion of Coordinated Carbon Monoxide into Carbon Dioxide via Oxygen-atom transfer from Coordinated Nitrite: Thermolysis of Ru(NO2)2(CO)2(PPh3)2
Doughty, David T.,Stewart, Robert P.,Gordon, Gilbert
, p. 3388 - 3395 (1981)
The thermolysis (111 deg C, toluene solution) of Ru(NO2)2(CO)2(PPh3)2 in the presence of excess PPh3 procced according to the stoichiometry Ru(NO2)2(CO)2(PPh3)2 + PPh3 -> Ru(NO2)2(PPh3)2 + CO2 + CO + Ph3PO.Two highly selective oxygen-atom transfer processes are involved in the overall thermolysis reaction: (i) Ru(NO2)2(CO)2(PPh3)2 -> Ru(ONO)(CO)(NO)(PPh3)2 + CO2; (ii) Ru(ONO)(CO)(NO)(PPh3)2 + PPh3 -> Ru(NO2)2(PPh3)2 + CO + Ph3PO.The intermediate complex Ru(ONO)(CO)(NO)(PPh3)2 was synthesized independently and has been characterized by analytical and spectral methods.The thermolysis of Ru(N18O2)2(CO)2(PPh3)2 unambiguosly establishes coordinated NO2- as the source of oxygen in the conversion of coordinated CO into CO2.Moreover, the extent of 18O enrichment in the CO2 product indicates that statistical scrambling of oxygen occurs between nitrogen and carbon atoms prior to the loss of CO2.The results of a double-label study involving the thermolysis of Ru(N18O2)2(CO)2(PPh3)2 and Ru(NO2)2(13CO2)2 are consistent with an intermolecular mechanism for oxygen-atom transfer from NO2- to CO.Additional mechanistic implications are described.
N-alkylation of amines by homogeneous ruthenium complexes in the presence of free diphosphines
Tamaddoni Jahromi, Bahareh,Kharat, Ali Nemati
, p. 3498 - 3508 (2014/01/06)
Chemoselective N-alkylation of amines by ruthenium complexes in the presence of free diphosphine ligands under mild conditions is described. Octyl amine and aniline were chosen as aliphatic and aromatic amines to investigate the effect of different phosphines, reaction times, and temperature on conversion, as well as selectivity towards related secondary and tertiary amines. After optimization of the reaction conditions, this catalytic system was used for N-alkylation of other amines and has shown moderate to very good yields. The reaction products were monitored by GC-MS. The crystal structure of [Ru(NO3)2CO(PPh3)2] with a monodentate and a bidentate nitrate was determined by X-ray crystallographic analysis.
