10.1021/om049619q.s001
Wilhelmus J. Hoogervorst
Wilhelmus J.
Hoogervorst
Kees Goubitz
Kees
Goubitz
Jan Fraanje
Jan
Fraanje
Martin Lutz
Martin
Lutz
Anthony L. Spek
Anthony L.
Spek
Jan Meine Ernsting
Jan Meine
Ernsting
Cornelis J. Elsevier
Cornelis J.
Elsevier
(Bis(imino)aryl)rhodium(III) Halide and Methyl
Compounds
American Chemical Society
2004
methyl
compound
aryl
rhodium
RhX 2
dihalide
imine moieties
isophthalaldimine
NCN
2004-09-27 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/_Bis_imino_aryl_rhodium_III_Halide_and_Methyl_Compounds/3323827
The synthesis and X-ray crystal structure of a number of aryl−rhodium dihalide and aryl−rhodium methyl halide complexes [RhX<sub>2</sub>(NCN)] and [RhX(CH<sub>3</sub>)(NCN)] with bis(imino)aryl
type tridentate NCN ligands are reported. These are interesting examples of compounds on
the reaction coordinate of C−halogen, halogen−halogen, and C−C bond-forming and bond-breaking reactions. Due to the strong C(sp<sup>2</sup>)−C(sp<sup>3</sup>) bond, only very few transition-metal
compounds having an aryl as well as a methyl group bonded to the same metal atom are
known and, usually, reductive elimination occurs. It has been shown that the imine moieties
of the isophthalaldimine ligand in the rhodium(III) dihalide compounds [RhX<sub>2</sub>(NCN)]
coordinate quite strongly, since the addition of an excess of pyridine or PPh<sub>3</sub> resulted in
their coordination to rhodium, not in substitution of the imine moieties. Transmetalation of
the rhodium(III) isophthalaldimine dihalide compounds [RhX<sub>2</sub>(NCN)] with Me<sub>2</sub>Zn provides
novel rhodium(III) methyl halide isophthalaldimine compounds [RhX(CH<sub>3</sub>)(NCN)]. These
diorganorhodium compounds are stable and do not give rise to reductive C−C coupling, which
must be partially ascribed to the relatively high electron density on the rhodium(III) center,
due to the strongly electron donating imine moieties.