Unexpected transfer of phenyl from a phenylbismuth complex to iridium in [Cp*IrCl₂]₂

Abstract

Tetranuclear [PhBi(pyzc)₂]₄·2(H₂O) (1) (where pyzc⁻ = 2-pyrazinecarboxylic acid) is easily obtained via reaction of BiPh₃ and Hpyzc under reflux. Treatment of 1 with [Cp*IrCl₂]₂ affords phenyliridium complex [Cp*Ir(Ph)(2-(NC₄H₃N)CO₂)] (2). Unexpected transfer of phenyl from 1 to iridium occurs. The structures of 1 and 2 are established by single-crystal X-ray diffraction. Each bismuth in 1 is in the center of distorted pentagonal pyramidal geometry, equatorially coordinating one κ²-N,O and one μ₂-(κ²-N,O),O′ pyzc, axially binding to phenyl. Complex 2 displays a typical piano-stool geometry with the metal center coordinated by Cp*, a terminal phenyl, and a chelating N,O-ligand. The UV–vis spectrum of 2 is described.

Graphical Abstract

Keywords:

• Tetranuclear
• Bismuth
• Iridium
• Pyrazinecarboxylate
• Phenyl transfer

Acknowledgement

This work was supported by the National Natural Science Foundation of China (project 21001118), Hunan Provincial Science and Technology Department (S2012R1040), and the Test Fund of Central South University for valuable equipments.