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Adams N, Bigmore HR, Blundell TL, et al. New titanium imido synthons: syntheses and supramolecular structures. Inorg Chem. 2005;44(8):2882-94doi: 10.1021/ic050011z.
Adams, N., Bigmore, H. R., Blundell, T. L., Boyd, C. L., Dubberley, S. R., Sealey, A. J., Cowley, A. R., Skinner, M. E., & Mountford, P. (2005). New titanium imido synthons: syntheses and supramolecular structures. Inorganic chemistry, 44(8), 2882-94. https://doi.org/10.1021/ic050011z
Adams, Nico, et al. "New titanium imido synthons: syntheses and supramolecular structures." Inorganic chemistry vol. 44,8 (2005): 2882-94. doi: https://doi.org/10.1021/ic050011z
Adams N, Bigmore HR, Blundell TL, Boyd CL, Dubberley SR, Sealey AJ, Cowley AR, Skinner ME, Mountford P. New titanium imido synthons: syntheses and supramolecular structures. Inorg Chem. 2005 Apr 18;44(8):2882-94. doi: 10.1021/ic050011z. PMID: 15819576.
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Inorg Chem. 2005 Apr 18;44(8):2882-94. doi: 10.1021/ic050011z.

New titanium imido synthons: syntheses and supramolecular structures.

Inorganic chemistry

Nico Adams, Helen R Bigmore, Timothy L Blundell, Catherine L Boyd, Stuart R Dubberley, Andrew J Sealey, Andrew R Cowley, Michael E G Skinner, Philip Mountford

Affiliations

  1. Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, UK.

PMID: 15819576 DOI: 10.1021/ic050011z

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.

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