1438662-20-4Relevant articles and documents
Group IV organometallic compounds based on dianionic "pincer" ligands: Synthesis, characterization, and catalytic activity in intramolecular hydroamination reactions
Luconi, Lapo,Rossin, Andrea,Motta, Alessandro,Tuci, Giulia,Giambastiani, Giuliano
, p. 4906 - 4921 (2013/05/21)
Neutral ZrIV and HfIV diamido complexes stabilized by unsymmetrical dianionic N,C,N′ pincer ligands have been prepared through the simplest and convenient direct metal-induced Caryl-H bond activation. Simple ligand modification has contributed to highlight the non-innocent role played by the donor atom set in the control of the cyclometallation kinetics. The as-prepared bis-amido catalysts were found to be good candidates for the intramolecular hydroamination/cyclization of primary aminoalkenes. The ability of these compounds to promote such a catalytic transformation efficiently (by providing, in some cases, fast and complete substrate conversion at room temperature) constitutes a remarkable step forward toward catalytic systems that can operate at relatively low catalyst loading and under milder reaction conditions. Kinetic studies and substrate-scope investigations, in conjunction with preliminary DFT calculations on the real systems, were used to elucidate the effects of the substrate substitution on the catalyst performance and to support the most reliable mechanistic path operative in the hydroamination reaction. Changing the order of the "factors" can (somehow) change the result! Neutral ZrIV and HfIV diamido complexes stabilized by unsymmetrical dianionic N,C,N′-pincer ligands have been prepared (see picture) and successfully employed as good catalyst candidates for the efficient and mild intramolecular hydroamination/cyclization of primary aminoalkenes. Copyright
