The 1-:-1 molar reactions at room temperature of MoCl5with aliphatic amines were investigated in dichloromethane. Pyrrolidine, diethylamine and dibenzylamine underwent dehydrogenative oxidation when allowed to react with MoCl5; the compounds [MoCl5NCH(CH2)3], 1, and [CH3CHNHEt][MoOCl4], 2, were isolated in moderate to low yields from MoCl5/pyrrolidine and MoCl5/NHEt2, respectively. The chloride-amide complex [MoCl4(NEt2)], 3, was afforded in 65% yield from MoCl5and Et2NSiMe3. The interaction of MoCl5with Me2NSiMe3was accompanied by activation of the solvent, and the complexes [MoCl3(NMe2)(κ2-Me2NCH2NMe2)], 4a, and [MoCl3(NMe)(κ2-Me2NCH2NMe2)], 4b, co-crystallized from the reaction mixture. The reactions of MoCl5with a series of primary amines afforded mixtures of products, and the Mo(vi) chloride imido complexes [MoCl4(NR)]2(R = Cy, 5a;tBu, 5b) were isolated in ca. 40% yield from MoCl5/NH2R (R = Cy,tBu). C-H bond activation may be viable in the reactions of MoCl5with tertiary amines: the compounds [(CH2Ph)2NCHPh]2[MoCl6]·CH2Cl2, 6, and [NHEt3]2[Mo2Cl10], 7, were obtained from MoCl5/tribenzylamine and MoCl5/triethylamine, respectively. Pyrrolidine and tribenzylamine underwent analogous activation pathways when allowed to react with [MoCl3OCH(CF3)2]2in the place of MoCl5. The isolated metal products were characterized by analytical and spectroscopic techniques, in addition the structures of 1, 2, 4, 5a, 6·CH2Cl2and 7 were ascertained by single crystal X-ray diffraction studies. The organic products were identified by NMR and GC-MS after hydrolysis of the reaction mixtures. DFT calculations were carried out in order to assist the IR assignments, and clarify structural and mechanistic aspects.
Bartalucci, N., Bortoluzzi, M., Marchetti, F., Pampaloni, G., Schoch, S., Zacchini, S. (2017). Unusual activation pathways of amines in the reactions with molybdenum pentachloride. NEW JOURNAL OF CHEMISTRY, 41(11), 4329-4340 [10.1039/c6nj03992h].
Unusual activation pathways of amines in the reactions with molybdenum pentachloride
Zacchini, Stefano
2017
Abstract
The 1-:-1 molar reactions at room temperature of MoCl5with aliphatic amines were investigated in dichloromethane. Pyrrolidine, diethylamine and dibenzylamine underwent dehydrogenative oxidation when allowed to react with MoCl5; the compounds [MoCl5NCH(CH2)3], 1, and [CH3CHNHEt][MoOCl4], 2, were isolated in moderate to low yields from MoCl5/pyrrolidine and MoCl5/NHEt2, respectively. The chloride-amide complex [MoCl4(NEt2)], 3, was afforded in 65% yield from MoCl5and Et2NSiMe3. The interaction of MoCl5with Me2NSiMe3was accompanied by activation of the solvent, and the complexes [MoCl3(NMe2)(κ2-Me2NCH2NMe2)], 4a, and [MoCl3(NMe)(κ2-Me2NCH2NMe2)], 4b, co-crystallized from the reaction mixture. The reactions of MoCl5with a series of primary amines afforded mixtures of products, and the Mo(vi) chloride imido complexes [MoCl4(NR)]2(R = Cy, 5a;tBu, 5b) were isolated in ca. 40% yield from MoCl5/NH2R (R = Cy,tBu). C-H bond activation may be viable in the reactions of MoCl5with tertiary amines: the compounds [(CH2Ph)2NCHPh]2[MoCl6]·CH2Cl2, 6, and [NHEt3]2[Mo2Cl10], 7, were obtained from MoCl5/tribenzylamine and MoCl5/triethylamine, respectively. Pyrrolidine and tribenzylamine underwent analogous activation pathways when allowed to react with [MoCl3OCH(CF3)2]2in the place of MoCl5. The isolated metal products were characterized by analytical and spectroscopic techniques, in addition the structures of 1, 2, 4, 5a, 6·CH2Cl2and 7 were ascertained by single crystal X-ray diffraction studies. The organic products were identified by NMR and GC-MS after hydrolysis of the reaction mixtures. DFT calculations were carried out in order to assist the IR assignments, and clarify structural and mechanistic aspects.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.