Organolanthanide constrained geometry complexes modified for catalysis: synthesis, structure, and aminoalkene hydroamination properties of a pyrrolidine-substituted constrained geometry organolutetium complex

摘要

The reaction of the organolutetium complex (CGC')LuCl3Li2(THF), (1; CGC' = [Me2Si(3-pyrrolidinyl-1-eta(5)-indenyl)('BuN)](2-)) with NaN(TMS)(2) provides a straightforward route to the halide-free organolutetium amido complex, (CGC')LuN(TMS)(2)(THF) (2). These new complexes were characterized by standard analytical methodology. The monomeric complex 2 crystallizes in the monoclinic space group P2(1)/c with four molecules in a cell of dimensions a = 11.1566(6) Angstrom, b = 14.9805(8) Angstrom, c = 22.18007(12) Angstrom, and beta = 90.0620(10)degrees. Complex 2 is an active precatalyst for the intramolecular hydroammation/cyclization of representative aminoalkenes with turnover frequencies as high as 205 h(-1) at room temperature. (C) 2004 Elsevier B.V. All rights reserved.