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A S=3/2 Cr(III) Complex In A Square‐Capping NHC Framework
Journal article   Peer reviewed

A S=3/2 Cr(III) Complex In A Square‐Capping NHC Framework

Michael R. Gau and Jeremiah J. Scepaniak
ChemistrySelect (Weinheim) , v 9(17), e202401830
03 May 2024
url
https://doi.org/10.1002/slct.202401830View
Published, Version of Record (VoR) Open

Abstract

carbene ligands chromium density functional calculations UV/Vis spectroscopy X-ray diffraction
Deprotonation of our pentadentate N‐Heterocyclic Carbene (NHC) ligand with lithium diisopropylamine in tetrahydrofuran and subsequent salt metathesis with CrCl3THF3 readily forms the complex PhCC4MeCrCl (1), a S=3/2 species in moderate yield. DFT calculations reveal three singly occupied molecular orbitals with π‐backbonding character to the square‐capping framework, UV‐Vis spectroscopy reveals 3 bands ascribed to d‐to‐d transitions, and cyclic voltammetry reveals an irreversible and quazi‐reversible reduction events as well as an irreversible oxidation event. We attempted to exchange the chloride ligand of 1 through salt‐metathesis with lithium phenylacetylide without success, the absence of reactivity is rationalized considering our XRD and DFT results. A S=3/2 CrIII complex supported by a dianionic pentadentate N‐heterocyclic carbene (NHC) ligand has been prepared. DFT studies reveal an electronic structure with dx2‐y2 orbital exhibiting unexpected π‐backbonding character towards the four equatorial NHC moieties. An attempted nucleophilic exchange of a chloride ligand for phenylacetylide proved unsuccessful and is rationalized in context of XRD and DFT results.

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Collaboration types
Domestic collaboration
Web of Science research areas
Chemistry, Multidisciplinary
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