Three-Coordinate Rhodium Complexes in Low Oxidation States
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Updated: Dec 30, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Víctor Varela-Izquierdo1, José A López1, Bas de Bruin2
1Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC, Universidad de Zaragoza, Pedro Cerbuna 12, 50009, Zaragoza, Spain.
Abstract:
The isolation of simultaneously low-coordinate and low-valent compounds is a timeless challenge for preparative chemists. This work showcases the preparation and full characterization of tri-coordinate rhodium(-I) and rhodium(0) complexes as well as a rare rhodium(I) complex. Reduction of [{Rh(μ-Cl)(IPr)(dvtms)}2 ] (1, IPr=1,3-bis(2,6-diisopropylphenyl)imidazolyl-2-ylidene; dvtms=divinyltetramethyldisiloxane) with KC8 gave the trigonal complexes K[Rh(IPr)(dvtms)] and [Rh(IPr)(dvtms)], whereas the cation [Rh(IPr)(dvtms)]+ results from their oxidation or by abstraction of chloride from 1 with silver salts. The paramagnetic Rh0 complex is a unique fully metal-centered radical with the unpaired electron in the dz2 orbital. The Rh(-I) complex reacts with PPh3 with replacement of the NHC ligand, and behaves as a nucleophile, which upon reaction with [AuCl(PPh3 )] generates the trigonal pyramidal complex [(IPr)(dvtms)Rh-Au(PPh3 )] with a metal-metal bond between two d10 metal centers.
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