104876-07-5Relevant academic research and scientific papers
Studies of molybdenum compounds. 5. Diethyl(2,2′ bipyridyl)dioxomolybdenum(VI) and other higher dialkyl derivatives of dioxomolybdenum(VI)
Schrauzer,Schlemper,Liu, Nan Hui,Wang, Qiguang,Rubin,Zhang, Xumu,Long, Xiping,Chin, Chong Shik
, p. 2452 - 2456 (2008/10/08)
The synthesis of diethyl(2,2′-bipyridyl)dioxomolybdenum(VI) and of other higher dialkyl derivatives of complexes of composition R2Mo(O)2(bpy) (R = C2H5, n- and i-C3H7, n- and i-C4H9, c-C5H9, c-C6H11; bpy = 2,2′-bipyridyl) from Br2Mo(O)2(bpy) and organomagnesium halides by a modification of a previously reported method is described. The complex (C2H5)2Mo(O)2(bpy) crystallizes from CH2Cl2 in the trigonal space group P3121 with a = b = 8.409 (3) ? and c = 40.69 (1) ?, with Z = 6, with 1/2 mol of CH2Cl2/mol of complex. Average bond distances in the planar Mo(O)2(bpy) moiety are similar to those observed in other complexes of this type (Mo=O = 1.702 (1) and Mo-N = 2.325 (12) ?). The in-plane O-Mo-O and N-Mo-N bond angles are also normal. Although the complex is much less stable thermally than the corresponding methyl derivative, the average Mo-C bond distances of 2.20 (2) ? are virtually the same as in the dimethyl species. However, the C-Mo-C bond angle of 151.9° is 2.9° wider than in the dimethyl and 3.8° narrower than in the dineopentyl derivative. These differences are attributed to interactions of the terminal ethyl hydrogen atoms with the oxygen atoms of the Mo(O)2 moiety. Thermolysis, photolysis, and acid hydrolysis of the Mo-C bonds produces mixtures of unrearranged olefins and alkanes as principal products. The cleavage of one Mo-C bond occurs mainly by way of β-elimination which induces the reductive cleavage of the other. Traces of higher hydrocarbons arising from Mo-C bond homolysis reactions are formed on thermolysis and photolysis of the solid complexes.
