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Pathways to Metal–Ligand Cooperation in Quinoline-Based Titanium(IV) Pincers: Nonelectrophilic N-methylation, Deprotonation, and Dihydropyridine Formation by Rosa Fandos; Antonio Rodríguez-Delgado; Ana Rodríguez; Iván Romero; Juan Ángel Organero; Eleuterio Álvarez is a Chemistry article available to read on EtoBox.

What is Pathways to Metal–Ligand Cooperation in Quinoline-Based Titanium(IV) Pincers: Nonelectrophilic N-methylation, Deprotonation, and Dihydropyridine Formation about?

A series of titanium(IV) complexes stabilized by quinolinebased pincer ligands have been synthesized and characterized. The reaction of [TiCp\*Me 3 ] with 8-hydroxy-2-quinolinecarboxaldehyde results in [TiCp\*Me-{κ 3 -N,O,O-(OCH)(8-O-N-Me-quin)}] (1), which shows an uncommon Nmethylation/dearomatization of the pyridinic ring; in contrast, when 8hydroxy-2-quinolinemethanol reacts with the same Ti(IV) trimethyl derivative, the expected monoalkyl complex [TiCp\*Me{κ 3 -N,O,O-(OCH 2 )(8-O-quin)}] (2) is formed. The pincer ligand in 2 can be dearomatized by deprotonation of the methylene fragment, yielding [TiCp\*Me{κ 3 -N,O,O-(OCH)(8-O-quin)}]-[Li(Et 2 O)] (3•Et 2 O) and [TiCp\*Me{k 3 -N,O,O-(OCH)(8-O-quin)}][Li(Py) 2 ] (3•2Py), or by incorporation of a hydride group into the para position of the pyridinic ring, giving [TiCp\*Me{κ 3 -N,O,O-(OCH 2 )(4-H-8-O-quin)}][Li• THF] (5). Compounds 1, [TiCp\*{κ 3 -N,O,O-(OCH 2 )(4-H-8-O-quin)}] 2 (6), and [TiCp\*{κ 3 -N,O,O-(OCH 2 )(4-H-8-O-quin)}] 2 [Li•THF] 2 (μ-O)] (7) have been studied by X-ray diffraction. Additionally, DFT quantum mechanical calculations were performed on complexes 1 and 2.

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Author

Rosa Fandos; Antonio Rodríguez-Delgado; Ana Rodríguez; Iván Romero; Juan Ángel Organero; Eleuterio Álvarez

Publisher

American Chemical Society (ACS)

Published

2021

Language

EN

Field

Chemistry (Physical Sciences)