Stability of metal–metal interactions in transmetallation intermediates based on electronics of bridging arene ligands determined through pyridine titrations
Date
2024
Authors
Version
OA Version
Published version
Citation
Abstract
In this contribution, we prepare the dinuclear complex [(CNCF)(PPh3)Pt–Au(PPh3)]+ (2-F) supported by an electron deficient derivative of 2,6-diphenylpyridine (CNC), 2,6-di(4-fluorophenyl)pyridine (CNCF). Solution state spectroscopic data and solid-state structural data reveals formation of the desired dinuclear complex occurs and that it remains intact in solution. The solid state structure of 2-F, compared to [(CNC)(PPh3)Pt–Au(PPh3)]+ (2), reveals a substantial change in the C–Au–P bond angle. We postulated that this change in bond angle arises due to a weaker interaction between [(PPh3)Au]+ and (CNCF)Pt(PPh3) (1-F) vs. (CNC)Pt(PPh3) (1). Through pyridine titration experiments, we demonstrate that the interaction is indeed weaker between [(PPh3)Au]+ and 1-Fvs. 1. Cyclic voltammetry (CV) experiments confirm that 1-F is less electron rich than 1. DFT calculations demonstrate that the HOMO of 1 and 1-F is not dz2, helping explain the differences in electrochemical behavior of 1 and 1-F and bonding between 1 and 1-F with [(PPh3)Au]+.
Description
License
This article is distributed under the terms of the Creative Commons Attribution-NonCommercial 3.0. This article has been published under a Read & Publish Transformative Open Access (OA) Agreement with RSC.