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Three‐Coordinate Rhodium Complexes in Low Oxidation States
Author(s) -
VarelaIzquierdo Víctor,
López José A.,
Bruin Bas,
Tejel Cristina,
Ciriano Miguel A.
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202000387
Subject(s) - rhodium , chemistry , trigonal crystal system , nucleophile , metal , ligand (biochemistry) , trigonal pyramidal molecular geometry , medicinal chemistry , stereochemistry , crystallography , catalysis , crystal structure , organic chemistry , biochemistry , receptor
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 KC 8 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 Rh 0 complex is a unique fully metal‐centered radical with the unpaired electron in the d z2 orbital. The Rh(‐I) complex reacts with PPh 3 with replacement of the NHC ligand, and behaves as a nucleophile, which upon reaction with [AuCl(PPh 3 )] generates the trigonal pyramidal complex [(IPr)(dvtms)Rh‐Au(PPh 3 )] with a metal–metal bond between two d 10 metal centers.