Titanium complexes of dialkanolamine ligands: Synthesis and structure

Zaitsev, K.V.; Karlov, S.S.; Selina, A.A.; Oprunenko, Y.F.; Churakov, A.V.; Neumueller, B.; Howard, J.A.K.; Zaitseva, G.S.

Abstract

Synthesis of the title compounds, viz. [RN(CH2CH2O)(CHR1CR2R3O)]Ti(OiPr)2 (13–15) and [RN(CH2CH2O)(CHR1CR2R3O)]2Ti (18–28), by the reaction of one ortwo equivalents of the corresponding dialkanolamines RN(CH2CH2OH)(CHR1CR2R3OH) (1–12) with Ti(OiPr)4 is reported. Other routes to [RN(CH2CH2O)(CHR1CR2R3O)]2Ti, such as the reaction of Ti(CH2Ph)4 with dialkanolamine and the reaction of TiCl4(THF)2 with dialkanolamine/Et3N were also tested. Dimeric titanocane 16, [PhCH2N(CH2CH2O)2Ti(OMe)2]2, was obtained from the reaction of one equivalentof dialkanolamine 3 with CpTi(OMe)3. PhCH2N(CH2CH2O)2Ti(OMenth)2 (17) was prepared from the transalkoxylation reaction of 15 with two equivalents of menthol. The composition and structures of all novel compounds were established by 1H and 13C NMR spectroscopy as well as elemental analysis data. The possible solution structure features of 13–28 are discussed. The single-crystal X-ray diffraction study oftitanocane 16 clearly indicates a dimeric structure for this compound in the solid state. According to X-ray data, compounds [PhCH2N(CH2CH2O)2]2Ti (19), [MeN(CH2CH2O)(CH2CHPhO)]2Ti (20), [MeN(CH2CH2O)(CH2CPh2O)]2Ti (23), erythro-[MeN(CH2CH2O)(CHPhCHPhO)]2Ti (24), threo-[MeN(CH2CH2O)(CHPhCHPhO)]2Ti (25), and {MeN(CH2CH2O)[CH(CH2)4CHO]}2Ti (27) possess a monomeric structure with a hexacoordinate titanium atom in the solid state. Among them complexes 19, 20, 23, 25, and 27 are characterized by a cis disposition of the nitrogen atoms in the coordination environment of the Ti atom, while nitrogen atoms in 24 occupy trans positions.

Citation

Zaitsev, K., Karlov, S., Selina, A., Oprunenko, Y., Churakov, A., Neumueller, B., …Zaitseva, G. (2006). Titanium complexes of dialkanolamine ligands: Synthesis and structure. European Journal of Inorganic Chemistry, 2006(10), 1987-1999. https://doi.org/10.1002/ejic.200501154

• Journal Article Type: Article
• Publication Date: 2006
• Journal: European Journal of Inorganic Chemistry
• Print ISSN: 1434-1948
• Publisher: Wiley-VCH Verlag
• Peer Reviewed: Peer Reviewed
• Volume: 2006
• Issue: 10
• Pages: 1987-1999
• DOI: https://doi.org/10.1002/ejic.200501154
• Keywords: Titanium, Alkoxides, Pentacoordination, Hexacoordination, Dialkanolamine complexes.
• Public URL: https://durham-repository.worktribe.com/output/1565635