Nitrile- and Isocyanide-derived Pd and Pt Complexes in Metal-mediated Synthesis and Catalytic C-C coupling

Abstract

Nitrile- and Isocyanide-derived Pd and Pt Complexes in Metal-mediated Synthesis and Catalytic C-C coupling Armando J.L. Pombeiro, a M. Fátima C.Guedes da Silva, a,b Maxim L. Kuznetsov, a Max N. Kopylovicha aCentro de Química Estrutural, Instituto Superior Técnico, Universidade Técnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. E-mail: pombeiro@ist.utl.pt bUniversidade Lusófona de Humanidades e Tecnologias, ULHT Lisbon, 1749-024 Lisbon, Portugal Konstantin V. Luzyanin Department of Chemistry, University of Liverpool, Crown St., Liverpool L69 7ZD, UK Vadim Yu. Kukushkin St.Petersburg State University, 198504 Stary Petergof, Russian Federation Organonitriles (NCR) and isocyanides (CNR) are small molecules which can be conveniently activated by Pd and Pt metal centres towards nucleophilic attack by a diversity of nucleophiles [1] to afford a plethora of tyes of organo-nitrogen species that in some cases can be liberated from the coordinating metals, in metal-mediated synthetic processes, whereas, in other cases, can be applied as catalysts, e.g., for carbon-carbon cross coupling reactions. The research lines being addressed herein will be illustrated [2-8] by the use of a variety of protic nucleophiles and acyclic or cyclic 1,3-dipoles to yield a diversity of complexes with N- or C-coordinated species derived from their coupling with the NCR or CNR ligands. The molecular structures and further reactions of the obtained complexes, which include isocyanide-derived aminocarbenes, are presented, as well as their application in Suzuki-Miyaura and Heck cross coupling reactions. The mechanisms of some of the coupling reactions are discussed on the basis of theoretical studies. Selected References [1] V. Yu. Kukushkin, A.J.L.Pombeiro, Chem. Rev., 2002, 102, 1771. [2] R.S. Chay, K.V. Luzyanin, V.Yu. Kukushkin, M.F.C. Guedes da Silva, A.J.L. Pombeiro, Organometallics, 2012, 31, 2379. [3] R.R. Fernandes, J. Lasri, M.F.C. Guedes da Silva, A.M.F. Palavra, J.A.L. da Silva, J.J.R. Fraústo da Silva, A.J. L. Pombeiro, Adv. Synth. Cat., 2011, 353, 1153. [4] M.L. Kuznetsov, V.Yu. Kukushkin, A.J.L. Pombeiro, J.Org.Chem., 2010, 75, 1474. [5] F.M.C. Menezes, M.L. Kuznetsov, A.J.L. Pombeiro, Organometallics, 2009, 28, 6593. [6] K.V. Luzyanin, A.G. Tskhovrebov, M.C. Maia, M.F.C. Guedes da Silva, A.J L. Pombeiro, V.Yu. Kukushkin, Organometallics, 2009, 28, 6559. [7] M.N. Kopylovich, J. Lasri, M.F.C. Guedes da Silva, A.J.L. Pombeiro, Dalton Trans., 2009, 3074. [8] M.N. Kopylovich, V. Yu. Kukushkin, M. Haukka, K.V. Luzyanin, A.J.L. Pombeiro, J. Am. Chem. Soc., 2004, 126, 15040. Acknowledgement: The co-authors of the cited references are greatly acknowledged. The work has been partially supported by the Fundação para a Ciência e a Tecnologia (FCT, Portugal) and the RFBR (Russia).