# Cyclometalated Platinum Compounds from Competing C–H/C–X Bond Activation Pathways

## TL;DR

This study explores how different halogens affect the formation of platinum compounds through competing chemical pathways.

## Contribution

The paper reveals distinct reaction outcomes based on halogen type during platinum complex formation.

## Key findings

- A six-coordinate platinum(IV) compound forms with bromine ligands.
- Chlorine ligands produce both platinum(IV) and platinum(II) species via C–H activation.
- DFT calculations align with experimental results on reaction pathway competition.

## Abstract

X–C^N^N (X = Br, Cl)
ligands were reacted with
[Pt2Me4(μ-SMe2)2], 1, resulting in a six-coordinate cyclometalated platinum­(IV)
compound
containing an anionic C^N^N ligand when X = Br and both a platinum­(IV)
and a platinum­(II) product when X = Cl. The platinum­(II) species was
formed by C–H activation, followed by reductive elimination
of methane. The platinum compounds were characterized by multinuclear
NMR spectroscopy and single-crystal X-ray diffraction (SCXRD). Photophysical
properties were explored by using UV/vis, emission, and transient
absorption (TA) spectroscopies. DFT and TDDFT calculations were performed
to examine the competition between C–H activation and C–X
oxidative addition and compared to experimental results.