Multicomponent Mechanochemical Synthesis of Cyclopentadienyl Titanium tert-Butoxy Halides, Cp x TiX y (O t Bu)4-(x+ y) (x, y = 1, 2; X = Cl, Br)

Nicholas C Boyde; Grant W Steelman; Timothy P Hanusa

doi:10.1021/acsomega.8b00943

Multicomponent Mechanochemical Synthesis of Cyclopentadienyl Titanium tert-Butoxy Halides, Cp _x TiX _y (O ^t Bu)_{4-(x+ y)} (x, y = 1, 2; X = Cl, Br)

ACS Omega. 2018 Jul 20;3(7):8149-8159. doi: 10.1021/acsomega.8b00943. eCollection 2018 Jul 31.

Authors

Nicholas C Boyde¹, Grant W Steelman¹, Timothy P Hanusa¹

Affiliation

¹ Department of Chemistry, Vanderbilt University, VU Station B #351822, Nashville, Tennessee 37235, United States.

Abstract

Titanium tert-butoxy halides of the formula Cp _x TiX _y (O ^t Bu)_4-(x+y) (x, y = 1, 2; X = Cl, Br) have been prepared thorough milling the reagents without solvent. In the case of the chloride derivatives, Cp₂TiCl₂ is used as a starting material; in the case of the bromides, a mixture of LiCp, TiBr₄, and Li[O ^t Bu] is used. The stoichiometric ratios of the starting materials are reflected in the major products of the reactions. Single-crystal X-ray structures are reported for Cp₂TiCl(O ^t Bu), Cp₂TiBr(O ^t Bu), and CpTiBr₂(O ^t Bu), as well as for Cp₂TiCl(O ⁱ Pr) and a redetermination of Cp₂TiCl(OMe). The tert-butoxy derivatives are notable for their nearly linear Ti-O-C angles (>170°) that reflect Ti-O π-bonding, an interpretation supported with density functional theory calculations.