Ruthenium Halide Complexes as N‐Alkylation Catalysts

Abstract

A range of ruthenium‐arene compounds with chloride, bromide or iodide ligands were prepared and tested as catalysts for the homogeneous redox neutral alkylation of tert‐butylamine with phenethyl alcohol, and compared to the previously reported catalyst [RuCl2(p‐cymene)]2, in the presence of the diphosphine 1,1′‐bis(diphenylphosphino)ferrocene (dppf). The best catalytic activities were obtained with ruthenium iodide compounds. The formation of either [RuX(p‐cymene)(dppf)][X] or [(RuX2(p‐cymene))2(dppf)] (X = halide) under the catalytic conditions employed was investigated.

Substitution of alcohols by N-nucleophiles via transition metal-catalyzed dehydrogenation

“…Water and hydrogen were generated as the only stoichiometric by-products, rendering this method highly atom-economic. It should be noted that the efficiency of BH substitution of alcohols by amines through transition metalcatalyzed dehydrogenation is often strongly dependent on metals, 46 ligand/solvent and selection, 47 and other factors. 48 2.1.2 Iridium catalysts.…”

“…147 These catalysts could be recycled with low ruthenium leaching. (46) The continuous flow substitution of alcohols by amines was tested by using the supported catalysts in a column reactor. The anti-Parkinson agent Piribedil (7) was thus synthesized in 98% yield.…”

Synthesis, Reactivity, and Coordination of Semihomologous dppf Congeners Bearing Primary Phosphine and Primary Phosphine Oxide Groups

“…The molecular structures of 10 ·THF·2CH 2 Cl 2 and 12 ·2CHCl 3 determined by X-ray crystallography (Figure ) were generally similar to that of [(L ∧ L)­{(η 6 -arene)­RuCl 2 } 2 ] (L ∧ L = dppf and fc­(CH 2 PPh 2 ) 2 ) and [(η 6 - p -cymene)­RuCl 2 (FcCH 2 PH 2 -κ P )] . The complex molecule in the structure of 10 ·THF·2CH 2 Cl 2 was situated on the crystallographic inversion center, which rendered the ferrocene cyclopentadienyls exactly parallel and brought their phosphine substituents and the ligated ruthenium fragments into anti positions.…”

Experimental insights into catalytic oxidation of 1,6-hexanediol to ε-caprolactone over (p-cymene)RuCl2(L) complexes in non-polar media

“…S4-S10 †). [44][45][46][47][48][49][50] The steric and electronic effects of the ligands could be derived from the different cone angles of the L P ligands or the other substituted groups of the pyridine ring for L N ligands.…”

“…The (p-cymene)RuCl 2 (L) where L = L P1-P5 , L N1 , L N2 , L N4 , or L N5 were prepared according to the literature. [44][45][46][47][48][49][50] Measurements 1 H and 13 C NMR spectra were acquired on a Bruker DPX-500 and JEOL Resonance JNM-ECZ500R spectrometer (500 MHz) using CDCl 3 and toluene-d 8 as a solvent. 13 C crosspolarization magic angle spinning (MAS) NMR spectra were recorded using a JEOL resonance JNM-ECZ500R spectrometer (400 MHz).…”