851516-36-4Relevant academic research and scientific papers
New titanium imido synthons: Syntheses and supramolecular structures
Adams, Nico,Bigmore, Helen R.,Blundell, Timothy L.,Boyd, Catherine L.,Dubberley, Stuart R.,Sealey, Andrew J.,Cowley, Andrew R.,Skinner, Michael E. G.,Mountford, Philip
, p. 2882 - 2894 (2008/10/09)
Reactions of Ti(NMe2)2Cl2 with a wide range of primary alkyl and arylamines RNH2 afforded the corresponding 5-coordinate imido titanium compounds Ti(NR)Cl2(NHMe 2)2 (R = tBu (1), iPr (2), CH 2Ph (3), Ph (4), 2,6-C6H3Me2 (5), 2,6-C6H3iPr2 (6), 2,4,6-C 6H2F3 (7), 2,3,5,6-C6HF4 (8), C6F5 (9), 4-C6H4Cl (10), 2,3,5,6-C6HCl4 (11), 2-C6H4CF 3 (12), 2-C6H4tBu (13)). The compounds 1-13 are monomeric in solution but in the solid state form either N-H...Cl hydrogen bonded dimers or chains or perfluorophenyl π-stacked chains, depending on the imido R-group. The compound 13 was also prepared in a one-pot synthesis from RNH2 and Ti(NMe2) 4 and Me3SiCl, Reaction of certain Ti(NR)Cl 2(NHMe2)2 compounds with an excess of pyridine afforded the corresponding bis- or tris-pyridine analogues [Ti(NR)Cl 2(py)x]y (x = 3, y = 1; x = y = 2), and the structure of Ti2(NC6F5)2Cl 2(μ-Cl)2(py)4 shows π-stacking of perfluorophenyl rings. Reaction of Ti(NMe2)2Cl2 with cross-linked aminomethyl polystyrene gave quantitative conversion to the corresponding solid-supported titanium imido complex. This paper represents the first detailed study of how supramolecular structures of imido compounds may be influenced by simple variation of the imido ligand N-substituent.
