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

The reaction of the organolutetium complex (CGC′)LuCl3Li2(THF), (1; CGC′ = [Me2Si(3-pyrrolidinyl-1-η5-indenyl)(tBuN)]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 P21/c with four molecules in a cell of dimensions a = 11.1566(6) Å, b = 14.9805(8) Å, c = 22.18007(12) Å, and β = 90.0620(10)°. Complex 2 is an active precatalyst for the intramolecular hydroamination/cyclization of representative aminoalkenes with turnover frequencies as high as 205 h−1 at room temperature.