The use of an amino-oxazolinate (NNox = kappa(2)-2,6-dimethylphenylamido-4(S)-isopropyloxazoline) as a chiral analogue to amidinate ligands in the chemistry of titanium was found to lead to undesired side reactions. The reaction of 2,6-dimethylphenylamido-4(S)-isopropyloxazoline with [Ti(NMe2)(4)] afforded the bis(amidinato) complex [ Ti( NNox) 2( NMe2) 2] ( 2) which was thermally converted to the ring-opened decomposition products [Ti(NNox) {kappa(3)-N( 2,6-C6H3Me2) C(NMe2)NC(Pr-i)CH2O}(NMe2)] (3) and [Ti {kappa(3)-N(2,6-C6H3Me2)C(NMe2)-NC(Pr-i) CH2O}(2)] (4). The NMR spectra of 4 recorded at low temperature displayed two sets of resonances corresponding to two symmetric isomers in a 2: 5 ratio, the probable geometries of which were established by ONIOM (QM/MM) simulations. To suppress ring opening of the oxazolines, their oxygen atom was formally replaced by a CH2 group in the synthesis of a series of amino-pyrroline protioligands 2-RN(H)(5-C4H5NR') (HNRNR'). Their reaction with [ Ti( NMe2) 4] gave the thermally stable complexes [Ti((NNR')-N-R)(2)(NMe2)(2)], of which three derivatives were characterized by X-ray diffraction. They are stereochemically dynamic and undergo reversible ligand rearrangements in solution, for which the activation parameters were determined by variable-temperature H-1 NMR spectroscopy.