title: New titanium imido synthons: syntheses and supramolecular structures.
abstract: Reactions of Ti(NMe(2))(2)Cl(2) with a wide range of primary alkyl and arylamines RNH(2) afforded the corresponding 5-coordinate imido titanium compounds Ti(NR)Cl(2)(NHMe(2))(2) (R = (t)Bu (1), (i)Pr (2), CH(2)Ph (3), Ph (4), 2,6-C(6)H(3)Me(2) (5), 2,6-C(6)H(3)(i)Pr(2) (6), 2,4,6-C(6)H(2)F(3) (7), 2,3,5,6-C(6)HF(4) (8), C(6)F(5) (9), 4-C(6)H(4)Cl (10), 2,3,5,6-C(6)HCl(4) (11), 2-C(6)H(4)CF(3) (12), 2-C(6)H(4)(t)Bu (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 pi-stacked chains, depending on the imido R-group. The compound 13 was also prepared in a "one-pot" synthesis from RNH(2) and Ti(NMe(2))(4) and Me(3)SiCl. Reaction of certain Ti(NR)Cl(2)(NHMe(2))(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 Ti(2)(NC(6)F(5))(2)Cl(2)(mu-Cl)(2)(py)(4) shows pi-stacking of perfluorophenyl rings. Reaction of Ti(NMe(2))(2)Cl(2) 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.
authors.affiliation: Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, UK.
authors.forename: Nico
authors.initials: N
authors.lastname: Adams
authors.forename: Helen R
authors.initials: HR
authors.lastname: Bigmore
authors.forename: Timothy L
authors.initials: TL
authors.lastname: Blundell
authors.forename: Catherine L
authors.initials: CL
authors.lastname: Boyd
authors.forename: Stuart R
authors.initials: SR
authors.lastname: Dubberley
authors.forename: Andrew J
authors.initials: AJ
authors.lastname: Sealey
authors.forename: Andrew R
authors.initials: AR
authors.lastname: Cowley
authors.forename: Michael E G
authors.initials: ME
authors.lastname: Skinner
authors.forename: Philip
authors.initials: P
authors.lastname: Mountford