Brouillet, Etienne V. and Kennedy, Alan R. and Krämer, Tobias and Mulvey, Robert E. and Robertson, Stuart D. and Stewart, Alexander and Towie, Stephen (2020) Synthesis, Structure, and DFT Analysis of the THF Solvate of 2‐Picolyllithium: A 2‐Picolyllithium Solvate with Significant Carbanionic Character. Zeitschrift für anorganische und allgemeine Chemie, 646 (13). pp. 726-733. ISSN 0044-2313

Preview

Download (915kB) | Preview

Abstract

Previous studies of different solvates of 2-methylpyridyllithium (2-picolyllithium) have uncovered electronic structures corresponding to aza-allyl and enamido resonance forms of the metallated pyridine-based compounds. Here, we report the synthesis and characterization of [2-CH2Li(THF)2C5H4N], a new THF solvate. X-ray crystallographic studies reveal a dimeric arrangement featuring a non-planar eight-membered [NCCLi]2 ring, in which the primary cation-anion interaction is between the central Li atom and the C atom of the deprotonated methyl group [length, 2.285(2) Å], suggesting a new carbanionic resonance structure for this 2-picolyllithium series. The significant carbanionic character of [2-CH2Li(THF)2C5H4N] was confirmed by gas-phase DFT calculations [B3LYP/6-311+G(d)] with the calculated electron density interrogated by means of quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses. For comparison these computational analyses were also performed on the literature structures of [2-CH2Li(2-Picoline)C5H4N] and [2-CH2Li(PMDETA)C5H4N]. In a reactivity study, [2-CH2Li(THF)2C5H4N] was found to undergo nucleophilic addition to pyridine to generate dipyridylmethane in a good yield.

Item Type:	Article
Keywords:	Synthesis; Structure; DFT Analysis; THF Solvate; 2-Picolyllithium; A 2-Picolyllithium Solvate; Carbanionic Character;
Academic Unit:	Faculty of Science and Engineering > Chemistry
Item ID:	16200
Identification Number:	https://doi.org/10.1002/zaac.202000006
Depositing User:	Tobias Kraemer
Date Deposited:	29 Jun 2022 08:26
Journal or Publication Title:	Zeitschrift für anorganische und allgemeine Chemie
Refereed:	Yes
URI:	Publisher
Use Licence:	This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

Repository Staff Only(login required)

Item control page

Downloads

Origin of downloads