Reactions of Heteroallenes with Salan-based Ti(IV) Complexes: A Joint Experimental and Computational Study

Chem Asian J. 2024 Feb 25:e202400165. doi: 10.1002/asia.202400165. Online ahead of print.ABSTRACTThe reaction of Ti(NMe2)4 with the salan ligand precursor H2N2O2H2 led to the formation of [(L*)Ti(NHMe2)2] (L* = N2O24-) 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-Namido 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-N 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.PMID:38403858 | DOI:10.1002/asia.202400165

Source: Chemistry, an Asian Journal - February 25, 2024 Category: Chemistry Authors: Joana Hip ólito Ricardo Meyrelles Boris Maryasin Luis G Alves Ana M Martins Source Type: research