[(NHC)(NHC(ewg))RuCl(2)(CHPh)] complexes with modified NHC(ewg) ligands for efficient ring-closing metathesis leading to tetrasubstituted olefins.
Imidazolium salts (NHC(ewg)HCl) with electronically variable substituents in the 4,5-position (H,H or Cl,Cl or H,NO(2) or CN,CN) and sterically variable substituents in the 1,3-position (Me,Me or Et,Et or iPr,iPr or Me,iPr) were synthesized and converted into the respective [AgI(NHC)(ewg)] complexes. The reactions of [(NHC)RuCl(2)(CHPh)(py)(2)] with the [AgI(NHC(ewg))] complexes provide the respective [(NHC)(NHC(ewg))RuCl(2)(CHPh)] complexes in excellent yields. The catalytic activity of such complexes in ring-closing metathesis (RCM) reactions leading to tetrasubstituted olefins was studied. To obtain quantitative substrate conversion, catalyst loadings of 0.2-0.5 mol % at 80 degrees C in toluene are sufficient. The complex with the best catalytic activity in such RCM reactions and the fastest initiation rate has an NHC(ewg) group with 1,3-Me,iPr and 4,5-Cl,Cl substituents and can be synthesized in 95 % isolated yield from the ruthenium precursor. To learn which one of the two NHC ligands acts as the leaving group in olefin metathesis reactions two complexes, [(FL-NHC)(NHC(ewg))RuCl(2)(CHPh)] and [(FL-NHC(ewg))(NHC)RuCl(2)(CHPh)], with a dansyl fluorophore (FL)-tagged electron-rich NHC ligand (FL-NHC) and an electron-deficient NHC ligand (FL-NHC(ewg)) were prepared. The fluorescence of the dansyl fluorophore is quenched as long as it is in close vicinity to ruthenium, but increases strongly upon dissociation of the respective fluorophore-tagged ligand. In this manner, it was shown for ring-opening metathesis ploymerization (ROMP) reactions at room temperature that the NHC(ewg) ligand normally acts as the leaving group, whereas the other NHC ligand remains ligated to ruthenium.
Sashuk
Volodymyr
V
Organometallic Chemistry and Homogeneous Catalysis, Petersenstr. 18, Technische Universität Darmstadt, 64287 Darmstadt, Germany.
Peeck
Lars H
LH
Plenio
Herbert
H