From Lithium Bis(trimethylsilyl)amide with Cyanoamine into Triazine Compounds: Synthesis and Structures of Lithium 6-((Trimethylsilyl)amido)-2,4-bis(d

1,3,5-Triazine heterocyclic π-conjugated systems are attractive and versatile for their structures and applications in medicinal chemistry, materials chemistry, and organic synthesis. Accordingly, the 2,4,6-trisubstituted 1,3,5-triazines have attracted much interest. 2,4,6-Triphenyl-1,3,5-triazine derivatives have been largely explored, and pyridyl-substituted 1,3,5-triazines such as 2,4,6-tris(2-pyridyl)-1,3,5-triazines have been extensively referenced. Recently, lanthanide 2,4,6-tris(2-pyridyl)-1,3,5-triazine complexes with visible light luminescence were reported. 2,4,6-Trimercapto-1,3,5-triazine can be used in wastewater treatment to remove heavy metals and also to prepare polynuclear trithiocyanurato-bridged metal complexes bearing bidentate chelating N and S heterocycles. Triprotic 2,4,6-tris(organoamino)-1,3,5-triazenes are promising potential multisite ligands. Moreover, several 1,2,4-triazines, bi(1,2,4-triazines), or transition-metal complexes with disubstituted triazine-based ligands and bi(1,3,5-triazine)ligands were also prepared. However, new and effective syntheses of 1,3,5-triazine heterocyclic rings under mild conditions are still of significance in modern organometallic and organic chemistry; moreover, organometallic derivatives of triazine are scarce and the numbers of accessible heterocyclic skeletons are still limited.

Addition reactions of lithium bis(trimethylsilyl)amide with dimethylcyanamide lead to novel lithium salts of 6-((trimethylsilyl)amido)-2,4-bis(dimethylamino)[1,3,5]triazines [LLi(D)]₂ (L = NC(NMe₂)NC(NMe₂)NC(NSiMe₃); D = Me₂NCN (1), Et₂O (2)) and to the Mn and Co complexes [LL′M] (L′ = N{N(SiMe₃)C(NMe₂)}₂; M = Mn (3), Co (4)). Their formation involves trimethylsilyl shifts, ring formation, and unusual Me₂NSiMe₃ elimination.

Meisu Zhou (et al.).From Lithium Bis(trimethylsilyl)amide with Cyanoamine into Triazine Compounds: Synthesis and Structures of Lithium 6-((Trimethylsilyl)amido)-2,4-bis(dimethylamino)[1,3,5]triazines and Their Manganese and Cobalt Complexes. Inorganic Chemistry. American Chemical Society. Apr 1, 2012. http://pubs.acs.org/doi/full/10.1021/ic201629a