Tris(2-pyridyl)amine copper (I) complexes: Simple and efficient catalysts for carbene and nitrene transfer reactions

INOR 235

Dolores Morales, moralesdolores.uo@uniovi.es1, Luis A. García, luangar@hotmail.com2, Héctor Martínez, martinezhector.uo@uniovi.es2, Julio Pérez, japm@uniovi.es2, Víctor Riera, vrg@uniovi.es3, and Daniel Miguel, dmsj@qi.uva.es4. (1) Departamento de Quimica Organica e Inorganica, I.U.Q.O.E.M.,Facultad de Quimica, Universidad de Oviedo, CSIC, C/ Julian Claveria, nº 8, 33006 Oviedo, Spain, (2) Departamento de Quimica Organica e Inorganica, I.U.Q.O.E.M.,Facultad de Quimica, Universidad de Oviedo, CSIC, C/ Julian Claveria, nº 8, 33006 Oviedo, Spain, (3) Facultad de Química, Universidad de Oviedo-CSIC, Departamento de Química Orgánica e Inorgánica- IUQOEM, Julián Clavería, 8, 33006 Oviedo, Spain, (4) Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47071 Valladolid, Spain
Copper complexes of tridentate tris(pyrazolyl)borates (CuTp) are some of the most useful catalysts for carbene and nitrene transfer (CNT) reactions. Therefore, there is an obvious interest in the exploration of other copper complexes of nitrogen-donor ligands as catalysts for these reactions. Ligands with pyridyl donor groups have been extensively employed in copper coordination chemistry, including the catalysis of CNT reactions. However, tridentate tris(2-pyridyl) ligands (TPy) have received little attention in copper chemistry, and their copper complexes were never used as catalysts for CNT reactions. Different studies suggest that a good catalyst for the above mentioned reactions should have a high electrophilic character, thus we have considered that a neutral tridentate N-donor ligand, such as tris(2-pyridyl)amine could provide a more electrophilic complex. In this context, we have prepared and characterized several Cu(I) complexes containing the tris(2-pyridyl)amine ligand in different stoichiometries, and we have tested their activities as catalysts in olefin cyclopropanation and aziridination using ethyl diazoacetate (EDA) and PhI=NTs as carbene and nitrene source, respectively. In addition, we have found that the same type of complexes functionalize O-H and N-H bonds (via Cu-catalyzed carbene insertion) and non-active C-H bonds such as those of alkanes and ethers by means of a carbene or nitrene insertion reactions.
 

Inorganic Catalysts
7:00 PM-10:00 PM, Sunday, August 19, 2007 BCEC -- Exhibit Hall - B2, Poster

Division of Inorganic Chemistry

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007