Reactions of Heteroallenes with Salan-based Ti(IV) Complexes: A Joint Experimental and Computational Study
Joana Hipólito1, Ricardo Meyrelles2,3,4, Boris Maryasin2,3
1Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais 1, 1049-001, Lisboa, Portugal.
Abstract:
The reaction of Ti(NMe2)4 with the salan ligand precursor H2N2O2H2 led to the formation of [(L*)Ti(NHMe2)2] (L*=N2O2 4-) that forms [(H2N2O2)TiCl2] upon reaction with two equiv. of Me3SiCl. [(L*)Ti(py)2] was obtained from the reaction of [Ti(NtBu)Cl2(py)3] with the sodium salt H2N2O2Na2. Treatment of [(L*)Ti(NHMe2)2] with two equiv. of tBuNCO led to the insertion of the isocyanate molecules into the Ti-Nsalan bonds with the formation of [{L*(N(tBu)CO)2}Ti]. Conversely, the reaction of [(H2N2O2)Ti(OiPr)2] with two equiv. of tBuNCO led to the insertion of one isocyanate molecule into a Ti-Nsalan bond with the formation of [{(HN2O2)(N(tBu)CO)}Ti(OiPr)]. Computational studies were performed to gain insight into the reactivity of isocyanates with salan-based Ti(IV) complexes.
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