کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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66458 | 48432 | 2010 | 8 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: Highly soluble dichloro, dibromo and dimethyl dioxomolybdenum(VI)-bipyridine complexes as catalysts for the epoxidation of olefins Highly soluble dichloro, dibromo and dimethyl dioxomolybdenum(VI)-bipyridine complexes as catalysts for the epoxidation of olefins](/preview/png/66458.png)
The reaction of solvent substituted MoO2X2(S)2 (X = Cl, S = THF; X = Br, S = DMF) complexes with one equivalent of bidentate nitrogen donor ligands at room temperature leads within a few minutes to the quantitative formation of complexes of the type [MoO2X2L2] (L = 4,4′-bis-methoxycarbonyl-2,2′-bipyridine, 5,5′-bis-methoxycarbonyl-2,2′-bipyridine, 4,4′-bis-ethoxycarbonyl-2,2′-bipyridine, 5,5′-bis-ethoxycarbonyl-2,2′-bipyridine). Treatment of the complexes [MoO2Cl2L2] with Grignard reagents at low temperatures yields dimethylated complexes of the formula [MoO2(CH3)2L2]. [MoO2Br2(4,4′-bis-ethoxycarbonyl-2,2′-bipyridine)], [MoO2Br2(5,5′-bis-methoxycarbonyl-2,2′-bipyridine)] and [MoO2Br2(5,5′-bis-ethoxycarbonyl-2,2′-bipyridine)] have been exemplary examined by single crystal X-ray analysis. The complexes were applied as homogenous catalysts for the epoxidation of cyclooctene with tert-butyl hydroperoxide (TBHP) as oxidising agent under solvent-free conditions. The complexes containing L = Cl have been additionally investigated with room temperature ionic liquids (RTILs) as solvents. The catalytic activity of the [MoO2X2L2] complexes in olefin epoxidation with tert-butyl hydroperoxide is on average very good. The main advantage of the synthesised complexes in comparison to previously reported complexes is their high solubility. This good solubility is apparently the reason that the catalytic potential of the compounds can unfold. The turnover frequencies (TOFs) in RTILs are even higher, showing the performance of the catalysts under optimised conditions.
MoO2X2(Solv)2 readily forms adducts with bipy-based ligands. If the bipy-ligands bear esters (C(O)OR) as functional groups good solubilities and high activities in olefin epoxidation are achieved.Figure optionsDownload high-quality image (86 K)Download as PowerPoint slide
Journal: Journal of Molecular Catalysis A: Chemical - Volume 331, Issues 1–2, 1 October 2010, Pages 117–124