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Formation of a nitrogen—carbon bond from N2 and CO. Influence of MgCl2 on the N2 reduction process in the system TiCl4/Mg

1984; Elsevier BV; Volume: 276; Issue: 2 Linguagem: Inglês

10.1016/0022-328x(84)80628-2

1872-8561

Piotr Sobota, Zofia Janas,

Inorganic Chemistry and Materials

TiCl4(THF)2 is reduced by Mg in tetrahydrofuran under N2 to TiNMg2Cl2(THF) (I), which reacts further with CO. As a result, TiCONMg2Cl2(THF) is obtained, which reacts with CH3I to produce (CH3)2NCOCH3 in 73% yield. This is indicative of the amide character of nitrogen in I. Upon reaction with I2, the amide nitrogen in I is oxidized to imide. The new compound, TiNMgCl(THF) (II), was found to form Ti(NCO)MgCl(THF) on reaction with CO. TiCl4(THF)2, recognized as a strong Lewis acid, detaches one Cl− from MgCl2(THF)2 formed in the reaction. The [MgCl(THF)n]+ cation influences the N2 reduction and determines the amide character of the nitrogen atom in species I.