RESUMEN
An efficient approach to the synthesis of olefin metathesis HG-type catalysts containing an NâRu bond in a six-membered chelate ring was proposed. For the most part, these ruthenium chelates can be prepared easily and in high yields based on the interaction between 2-vinylbenzylamines and Ind II (the common precursor for Ru-complex synthesis). It was demonstrated that the increase of the steric volume of substituents attached to the nitrogen atom and in the α-position of the benzylidene fragment leads to a dramatic decrease in the stability of the target ruthenium complexes. The bulkiest iPr substituent bonded to the nitrogen atom or to the α-position does not allow the closing of the chelate cycle. N,N-Diethyl-1-(2-vinylphenyl)propan-1-amine is a limiting case; its interaction with Ind II makes it possible to isolate the corresponding ruthenium chelate in a low yield (5%). Catalytic activity of the synthesized complexes was tested in RCM reactions and compared with α-unsubstituted catalysts obtained previously. The structural peculiarities of the final ruthenium complexes were thoroughly investigated using XRD and NMR analysis, which allowed making a reliable correlation between the structure of the complexes and their catalytic properties.
RESUMEN
The title compound, [RuCl2(C33H43N3O)], is an example of a new generation of N,N-dialkyl ruthenium catalysts with an N-Ru coordination bond as part of a six-membered chelate ring. The Ru atom has an Addison τ parameter of 0.244, which indicates a geometry inter-mediate between square-based pyramidal and trigonal-bipyramidal. The complex shows the usual trans arrangement of the two chlorides, with Ru-Cl bond lengths of 2.3515â (8) and 2.379â (7)â Å, and a Cl-Ru-Cl angle of 158.02â (3)°. One of the chlorine atoms and the atoms of the 2-meth-oxy-N-methyl-N-[(2-methyl-phen-yl)meth-yl]ethane-1-amine group of the title complex display disorder over two positions in a 0.889â (2): 0.111â (2) ratio.