84779-39-5Relevant academic research and scientific papers
Chlorophosphines as auxiliary ligands in ruthenium-catalyzed nitrile hydration reactions: Application to the preparation of β-ketoamides
González-Fernández, Rebeca,González-Liste, Pedro J.,Borge, Javier,Crochet, Pascale,Cadierno, Victorio
, p. 4398 - 4409 (2016)
The catalytic hydration of nitriles into amides, in water under neutral conditions, has been studied using a series of arene-ruthenium(ii) complexes containing commercially available chlorophosphines as auxiliary ligands, i.e. compounds [RuCl2(η6-p-cymene)(PR2Cl)] (R = aryl, heteroaryl or alkyl group). In the reaction medium, the coordinated chlorophosphines readily undergo hydrolysis to generate the corresponding phosphinous acids PR2OH, which are well-known "cooperative" ligands for this catalytic transformation. Among the complexes employed, best results were obtained with [RuCl2(η6-p-cymene){P(4-C6H4F)2Cl}]. Performing the catalytic reactions at 40 °C with 2 mol% of this complex, a large variety of organonitriles could be selectively converted into the corresponding primary amides in high yields and relatively short times. The application of [RuCl2(η6-p-cymene){P(4-C6H4F)2Cl}] in the preparation of synthetically useful β-ketoamides is also presented.
Synthesis and unexpected reactivity of [Ru(η 6-cymene)Cl2(PPh2Cl)], leading to [Ru(η 6-cymene)Cl2(PPh2H)] and [Ru(η 6-cymene)Cl 2 (PPh2OH)] complexes
Pandiakumar, Arun Kumar,Samuelson, Ashoka G
, p. 1329 - 1338 (2015/11/09)
The reaction of [Ru(η 6-cymene)Cl2]2 and PPh2Cl in the ratio 1:2 gives a stable [Ru(η 6-cymene) Cl2(PPh2Cl)] complex. Attempts to make the cationic [Ru(η 6-cymene)Cl(PPh2Cl)2]Cl with excess PPh2Cl and higher temperatures led to adventitious hydrolysis and formation of [Ru(η 6-cymene)Cl2(PPh2OH)]. Attempts to make a phosphinite complex by reacting [Ru(η 6-cymene)Cl2]2 with PPh2Cl in the presence of an alcohol results in the reduction of PPh2Cl to give [Ru(η 6-cymene)Cl2(PPh2H)] and the expected phosphinite. The yield of the hydride complex is highest when the alcohol is 1-phenyl-ethane-1,2-diol. All three half-sandwich complexes are characterized by X-ray crystallography. Surprisingly, the conversion of chlorodiphenylphosphine to diphenylphosphine is mediated by 1-phenyl-ethane-1,2-diol even in the absence of the ruthenium half-sandwich precursor. [Figure not available: see fulltext.]
Phosphido-bridged mixed-metal (Ru/Co) compounds via the reaction of (arene)RuCl2(PPh2X) (X = H, Cl) with Co2(CO)8: X-ray structure of RuCo2(μ-PPh2)2(μ-CO)(CO)7
Regragui, Rachid,Dixneuf, Pierre H.,Taylor, Nicholas J.,Carty, Arthur J.
, p. 1020 - 1025 (2008/10/08)
A strategy for the synthesis of heterobi- and heterotrinuclear phosphido-bridged complexes via the reactions of the readily available η6-arene compounds (p-cymene)RuCl2(PPh2X) (X = H, Cl) with Co2(CO)8 is described. This route has afforded heterobinuclear (CO)4Ru(μ-PPh2)Co(CO)3 (3), (p-cymene)(CO)Ru(μ-PPh2)Co(CO)3 (7), small amounts of Ru2(μ-PPh2]2(CO)6 (4), and the heterotrinuclear clusters Ru2Co(μ-PPh2)(CO)10 (5) and RuCo2(μ-PPh2)2(CO)8 (6). These compounds have been characterized by microanalysis and mass, infrared, and NMR (1H, 13C, 31P) spectroscopy. Single crystals of RuCo2(μ-PPh2]2(CO)8 are monoclinic of space group P21/n with a = 12.714 (2) A?, b = 15.600 (3) A?, c = 17.246 (3) A?, β = 108.33 (1)°, and Z = 4. The structure was solved and refined by using 3610 unique, observed reflections measured on a Syntex P21 diffractometer to R and Rw values of 0.034 and 0.039. In the triangular cluster the trans axial PPh2 groups bridge the Ru-Co(1) and Co(1)-Co(2) edges with a semibridging CO group across the remaining Ru-Co bond.
