Sala de Grados. Facultad de Ciencias 16/06/2014  12:00h.

"Advances in α elimination:
Catalytic organoelement synthesis"

Prof. Roy Waterman
University of Vermont, USA

Hora: 12:00 h
Fecha: 16 de junio 2014
Lugar: Sala de Grados, Edif. A Facultad de Ciencias

 

Advances in α Elimination: Catalytic Organoelement Synthesis
Rory Waterman
Department of Chemistry, University of Vermont
Burlington, USA
Rory.Waterman@uvm.edu. http://www.uvm.edu/~waterman

 

Advances in α Elimination: Catalytic Organoelement Synthesis

After observation of α-arsinidene elimination from triamidoamine-supported zirconium complexes and reports of α-stannylene and -stibinidene elimination from group 4 metallocenes by Tilley, an expansion of the elements that participate in this rare class of deinsertion reactions has been sought. Triamidoamine-supported zirconium complexes have been limited in effecting α elimination for lighter elements using, for example, silanes or phosphines as substrates. However, silanes with π-donating substituents, RXSiH₂ (X = NMe₂, Cl, etc), do react with [κ-N,N,N,N,C-(Me₃SiNCH₂CH₂)₂NCH₂CH₂NSiMe₂CH₂]Zr (1) to give (N₃N)ZrX (N₃N = N(CH₂CH₂NSiMe₃)₃^3–) with evidence of silylene formation. Furthermore, catalytic N–Si dehydrocoupling using triamidoamine-supported zirconium complexes has provided an in situ substrate, RXSiH₂, for α-silylene elimination. In select cases, the silylene fragment can be intercepted by an unsaturated organic substrate. Yet more success in organoelement synthesis has been realized recently with the use of iron catalysts. These compounds appear to dehydrocouple phosphines by α-phosphinidene elimination and can engage in catalytic preparation of phospholes from primary phosphines and either alkynes or dienes.

 

Rory Waterman completed his B.S. degree in chemistry at the University of Rochester in 1999. In 2004, he earned a Ph.D. degree in chemistry at The University of Chicago under Professor Gregory L. Hillhouse, studying the organometallic chemistry of three-coordinate nickel complexes. From 2004 to 2006, he was a Miller Institute for Basic Research in Science Research Fellow in the laboratories of Professor T. Don Tilley, investigating α elimination and E–H bond activation chemistry. He is currently Associate Professor of Chemistry at the University of Vermont, with interests in synthetic inorganic and organometallic chemistry, catalysis, and metal–ligand multiple bonding.