Interactional Features of (RO) <sub>4</sub> Ti Species and Their Zr and Hf Analogues

E Elisabetta Venturin (Department of Chemistry Materials Chemical Engineering “Giulio Natta” Politecnico di Milano via Mancinelli 7 Milano 20131 Italy) R Rosa M. Gomila (Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, Palma 07122, Baleares, Spain) R Roberta Bertani (Department of Industrial Engineering University of Padova via F. Marzolo 9 Padova 35131 Italy) A Andrea Pizzi (Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, via E. Bassini 6, 20133 Milano, Italy) P Paolo Sgarbossa (Department of Industrial Engineering University of Padova via F. Marzolo 9 Padova 35131 Italy) A Arun Dhaka (Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, via E. Bassini 6, 20133 Milano, Italy) A Antonio Frontera (Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, Palma 07122, Baleares, Spain) G Giuseppe Resnati (Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, via E. Bassini 6, 20133 Milano, Italy)

Abstract

Abstract Tetroxides of Group 4 elements are benchmark catalysts for aldol reactions and oxidation processes, achieving high yields and regio‐, diastereo‐, and enantioselectivities. Our computational analyses and experimental studies, performed in solution and solid, consistently reveal that these tetroxides form attractive interactions with lone pair compounds exhibiting distinctive σ‐hole bond features. We propose naming these novel bondings as titan bonds (TnBs). These new insights into Ti/Zr/Hf tetroxide interactions may significantly aid in designing more effective catalysts with enhanced selectivities.

Article Details

Volume / Issue Vol. 64, Issue 45
Published November 03, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (8)

E

Elisabetta Venturin

Department of Chemistry Materials Chemical Engineering “Giulio Natta” Politecnico di Milano via Mancinelli 7 Milano 20131 Italy

R

Rosa M. Gomila

Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, Palma 07122, Baleares, Spain

R

Roberta Bertani

Department of Industrial Engineering University of Padova via F. Marzolo 9 Padova 35131 Italy

A

Andrea Pizzi

Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, via E. Bassini 6, 20133 Milano, Italy

P

Paolo Sgarbossa

Department of Industrial Engineering University of Padova via F. Marzolo 9 Padova 35131 Italy

A

Arun Dhaka

Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, via E. Bassini 6, 20133 Milano, Italy

A

Antonio Frontera

Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, Palma 07122, Baleares, Spain

G

Giuseppe Resnati

Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, via E. Bassini 6, 20133 Milano, Italy