Electronic and Steric Manipulation of the Agostic Interaction in benzo[<i>h</i>]quinoline Complexes of Pd(II) and Implications for the Formation of η¹‐Pd–C Bonds

Nielson, Alastair J ORCID: 0000-0003-2086-3295, Harrison, John A, Sajjad, M Arif and Schwerdtfeger, Peter (2020) Electronic and Steric Manipulation of the Agostic Interaction in benzo[<i>h</i>]quinoline Complexes of Pd(II) and Implications for the Formation of η¹‐Pd–C Bonds. European Journal of Inorganic Chemistry, 2020 (27). pp. 2639-2650.

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Abstract

<jats:p>Structures and properties were obtained by density functional (DFT) calculations for the complexes [PdCl<jats:sub>2</jats:sub>(L)] (L = benzo[<jats:italic>h</jats:italic>]quinolines) containing aromatic ring agostic interactions. The inflexibility of the benzenoid rings of the ligands keep the structures of the complex relatively constant when electron withdrawing substituents are added to the aromatic ring <jats:italic>para</jats:italic> to the agostic carbon but electron donation causes a change to η<jats:sup>1</jats:sup>‐Pd–C bond complexes in which agostic donation is significantly reduced and π‐syndetic donation no longer features. Increasing the steric size at the α‐carbon through the series H, Me, CHMe<jats:sub>2</jats:sub>, CMe<jats:sub>3</jats:sub> or Ph, changes the manner in which the ligand sits in relation to the coordination plane but a change in the way the nitrogen atom of the ligand tilts in relation to the coordination plane does not effectively reduce the agostic or syndetic donations. CPh<jats:sub>3</jats:sub> reduces the agostic donation but not the syndetic donation and C(Ph‐2,6‐Me<jats:sub>2</jats:sub>)<jats:sub>3</jats:sub> turns both donations off and installs η<jats:sup>2</jats:sup> π‐donation on one aromatic ring. Placing <jats:italic>ortho</jats:italic>‐substituents on the ring can influence the interplay of electronic and steric effects when η<jats:sup>1</jats:sup>‐Pd complexes are formed.</jats:p>

Item Type:	Article
Depositing User:	Symplectic Admin
Date Deposited:	03 Jun 2020 07:59
Last Modified:	18 Sep 2023 18:58
DOI:	10.1002/ejic.202000348
Related URLs:	Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3089363