Redox and oxo‐abstraction Reactions of Silylamine with MoOCl₄

Abstract

Trimethylsilyldiethylamine Me3SiNEt2 and MoOCl4 (1:1) undergo a free radical redox reaction in CH2Cl2 or Et2O to form MoCl3O(HNEt2). Reduction occurs even in aprotic media like CCl4 and CS2 to give MoV complexes Mo2Cl6O2(N2Et4) and Mo2Cl6O2[(SCNEt2)2S2], respectively. A 2:1 reaction in nonionizing protic solvents undergoes redox cum cleavage to provide MoCl2O(NEt2) (HNEt2) but a reaction at reflux temperature in 1,2‐dichloroethane leads to diethylammonium salt, [Et2NH2][MoCl4O(HNEt2)]. Higher molar reactions (3:1, 4:1) in CH2Cl2 or Et2O are associated with redox reaction as well as oxygen atom abstraction to form de‐oxo MoIV complex MoCl3(NEt2)(HNEt2)2, whereas, a 3:1 reaction in CS2 forms Mo2Cl4O(S2CNEt2)4. Compounds have been characterized by elemental analyses, redox titration, magnetic moment, conductance, infrared, electronic absorption and 1H‐NMR measurements.

Reactions of MoOCl4 with 1-Methylimidazole, 1,4-Diaminobutane, 2-Methylpyridine, 2-Methylpiperidine, Trimethylsilylimidazole and 1-Methylpyrrolidine

“…C=N Str. in [3] was observed at higher frequency at 1625 cm -1 . C-N stretching in [3] was observed at lower frequency at 1288.3 cm -1 (Table 4).…”

“…in [3] was observed at higher frequency at 1625 cm -1 . C-N stretching in [3] was observed at lower frequency at 1288.3 cm -1 (Table 4). All these observations indicate the presence of 2-methylpyridine in [3].…”

“…Ring C-H stretching in 2-methylpyridine [19][20][21][22] are obtained at 3137 cm -1 and 3066 cm -1 . Ring C-H stretching in [3] are observed at higher frequencies 3296.0 cm -1 and 3081.0 cm -1 . C=N Str.…”

“…C-N stretching in [3] was observed at lower frequency at 1288.3 cm -1 (Table 4). All these observations indicate the presence of 2-methylpyridine in [3]. A strong Mo=O stretching at 980.0 cm -1 in [3] shows the presence of terminal Mo=O 16,17 .…”

“…Reactions may yield addition, substitution, reduction, rearrangement and polymerization products. Reactions of MoOCl 4 in solvent CH 2 Cl 2 have been reported [1][2][3][4][5] by the author. Ligands are poorly soluble in solvent CH 2 Cl 2 so reactions of MoOCl 4 were also carried out and reported [6][7][8][9][10][11] by the author in CH 3 CN medium.…”