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Abstract Molecular titanosilicates (t BuO 3) 3 SiO 2 Ti (NR 2) 2 (1, R=Et; 2, R=Me) and (t BuO 3) 3 SiO 3 TiNR 2 (TSA1, R=Et; 3, R=Me) were obtained from the reaction between silanol (t BuO 3) 3 SiOH (S1) and titanium amides Ti (NR 2) 4 (R=Et, R=Me). Additionally, the reaction of 3 and TSA1 with CO 2 led to the exclusive formation of carbamates (t BuO) 3 SiO 3 Ti (O 2 CNR 2) (4, R=Et; 5, R=Me). The molecular structure of 5 confirmed the proposed connectivity and presence of SiO 4 and Ti (O 2 CNR 2) units. In compound 4, titanium is coordinated to five oxygen atoms belonging to one bidentate carbamate group and three silicate ligands in a distorted square‐base pyramidal geometry. Also, we have performed DFT calculations and QTAIM analysis to study the distribution of the electron density in the carbamate (t BuO) 3 SiO 3 Ti (O 2 CNEt 2) (4) and salt (t BuO) 3 SiO 3 TiO (H 2 NMe 2) 6 which was obtained by the hydrolysis of compound 5.
Pérez‐Pérez et al. (Mon,) studied this question.