The phenolic reagents 2-(inden-3-yl)-4,6-di-tert-butylphenol (1) and its 2-methyl (2), 1,2-dimethyl (3), 2,4,7-trimethyl (4) and 1,2,4,7-tetramethyl (5) derivatives have been obtained. The solid-state structures of 2, 3 and 4 have been determined by X-ray diffraction and torsion angles (between the vinyl group and phenoxy ring) of 57, 61 and 79° measured. Both the (aR) and (aS) forms of the ligands are present in the solid state. Solution ¹H NMR spectra show that rotation about the indenyl–phenoxy bond is facile for 1 but introduction of the 2-methyl substituent leads to restricted rotation on the NMR timescale. In the crystals of 3 analyzed, only the (aS,S) and (aR,R) forms were present, with the 1-methyl group pointing away from the OH group. In the ¹H and ¹³C NMR spectra of 3 and 5 there are two, equal intensity sets of signals. Hence, both diastereoisomeric forms are present in equal concentrations in solution and two sharp OH singlets are observed for 3 even at 130 °C in p-xylene-d₁₀. Reaction of the phenols 1–4 with [CpTiCl₃] in the presence of pyridine has previously generated the corresponding mono-aryloxides 7–10 with no evidence of the de-protonation of the indenyl ring in these reactions. In all four compounds both the (aR) and (aS) forms are present within the unit cells. Variable temperature NMR studies of 7 allow the barrier to inden-3-yl rotation (enantiomer interconversion) to be estimated at 13.9(5) kcal mol⁻¹ (at 20 °C). In solution only one major set of ¹H and ¹³C NMR resonances were observed for 1,2-dimethyl derivative 9. Hence, it appears that replacement of the phenolic proton by the much bulkier [CpTiCl₂] unit destabilizes the (aS,R) and (aR,S) forms in solution. Attempted de-protonation of the inden-3-yl ring in 7 by treatment with n-BuLi or MeLi did not lead to the formation of chelate rings. Instead formation of a Ti(III) dinuclear compound 11 and dimethyl derivative 12 occurred. The barrier to indenyl rotation in 12 can be estimated to be 13.4(5) kcal mol⁻¹ at −5 °C, slightly lower than that measured for the dichloride 7. Reaction of [CpTiCl₃] with the di-lithio (doubly deprotonated ligand) did lead to the formation of a chelated indenyl-phenoxide derivative 13. In the solid state only the (pS,R) and (pR,S) forms were observed (indenyl oriented towards the Cp group, and in solution only one set of ¹H and ¹³C NMR signals were observed indicating the presence of this single diastereoisomer. The bonding of the indenyl group and Cp ligands in 13 have been compared.