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Reactions of [RuCl2(PPh3)3] with Nitron and with the “Enders Carbene”: Access to Ruthenium(III) NHC Complexes
journal contribution
posted on 2014-01-13, 00:00 authored by Sandra Hitzel, Christian Färber, Clemens Bruhn, Ulrich SiemelingThe reactions of [RuCl2(PPh3)3] with the “Enders carbene”
1,3,4-triphenyl-1,2,4-triazol-5-ylidene
(1) and the “instant carbene” Nitron (2) respectively afforded the RuII chelates [RuCl(3)(PPh3)2] (3 = 3,4-diphenyl-1-o-phenylene-1,2,4-triazol-5-ylidene) and [RuCl(4)(PPh3)2] (4 = 4-phenyl-3-phenylamino-1-o-phenylene-1,2,4-triazol-5-ylidene) in a process involving
the ortho metalation of the 1-Ph group of the respective carbene ligand.
It proved possible to synthesize [RuCl(3)(PPh3)2] more conveniently in higher yield by using the stable
carbene precursor 5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole (MeO-1-H) instead of the free carbene 1 in the presence of triethylamine to trap the HCl generated
by the ortho metalation. Aerobic oxidation of the RuII chelates
in the presence of chloride ions furnished [RuCl2(3)(PPh3)2] and [RuCl2(4)(PPh3)2], which are rare examples
of RuIII NHC complexes. The crystal structures of all four
complexes were determined by single-crystal X-ray diffraction studies.
In addition, the crystal structure of the hydrochloride of Nitron
was also determined. In the RuII chelates, the pentacoordinate
metal center is in a distorted-square-pyramidal environment with the
carbon atom of the ortho-metalated 1-Ph group occupying the apical
position. The coordination sphere of the RuIII chelates
is complemented by a second chlorido ligand, which is positioned trans to this carbon atom.