Lithium and Dilithium Guanidinates, a Starter Kit for Metal Complexes Containing Various Mono- and Dianionic Ligands

Comparative studies of the synthesis of lithium guanidinates via nucleophilic addition of lithium amides to carbodiimides were performed. Four combinations of small or sterically crowded carbodiimide and sterically crowded lithium amide or lithium amide containing an adjacent amino donor group give ten different types of complexes. In particular, 2,6-[(CH3)2CH]2C6H3NHLi (DipNHLi, 1) reacts with (CH3)2CHN═C═NCH(CH3)2 upon the formation of the dissymmetric dimeric complex 2 with four-coordinate Li atoms. In contrast, 1 with DipN═C═NDip gives the mononuclear lithium guanidinate 3 with two-coordinate lithium by κ1-guanidinate, solvent molecule, and additional interaction with a π-electron cloud of one of the Dip groups. Analogous reactions of 2-[(CH3)2NCH2]C6H4NHLi (7) yield complexes 8 and 9, where the adjacent amino donors are always coordinated. Further deprotonation of 2, 3, 8, and 9 leads to dilithium guanidinates(2-)-4, 5, 10, and 11, among which only 5, containing three Dip groups, is monomeric with contacts to two π-electron systems of Dip groups. The rest of the complexes are tetranuclear with different structural patterns. In the central parts of molecules, toward which the nitrogen atoms of the guanidinates are oriented, lithium atoms are usually pseudotetrahedral, but trigonal in peripheral parts. Adjacent solvent molecules, chelating amino groups, and π-electron systems of Dip groups are coordinated in order to complete coordination polyhedra. Complexes 4 and 5 deoligomerize in solution upon the formation of fluxional monomeric dilithium species. Conversely, 11 is a dimer in solution due to the strong donation of an amino group. The silylated lithium amide {2-[(CH3)2NCH2]C6H4}[(Si(CH3)3]NLi (12) reacts with both carbodiimides to give dinuclear 13 obtained from diisopropylcarbodiimide and monomeric 14 from the second carbodiimide. Complexes 13 and 14 structurally resemble 8 and 9, with the highest degree of the localization of π-electron density within the N3C guanidinate system, η3-contact to the Dip ring, and a lack of the solvent molecule in 14.