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Updated: Apr 5, 2026

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Isocyanate deinsertion from κ(1)-O amidates: facile access to perfluoroaryl rhodium(I) complexes
Marcus W Drover1, Laurel L Schafer1, Jennifer A Love1
1Department of Chemistry, The University of British Columbia, Vancouver, Canada. jenlove@chem.ubc.ca.
Abstract:
Reaction of the amidate ligand salt, Na[N(Dipp)C(O)C6F5] () (Dipp = 2,6-diisopropylphenyl) with [Rh(NBD)Cl]2 (NBD = norbornadiene) results in formation of the dirhodium(i) complex [Rh2{μ2-N,O-N(Dipp)C(O)C6F5}2(NBD)2] (). Reaction of with PCy3 at room temperature provides an equilibrium mixture of the geometric isomers (E/Z)-[Rh{κ(1)-O-N(Dipp)C(O)C6F5}(NBD)(PCy3)] (E/Z-). Treatment of with 3 equiv. of CNXyl (Xyl = 2,6-dimethylphenyl) gives the κ(1)-O complex [Rh{κ(1)-O-N(Dipp)C(O)C6F5}(CNXyl)3] () while use of 3 equiv. of PPh3 provides the κ(2)-complex [Rh{κ(2)-N,O-N(Dipp)C(O)C6F5}(PPh3)2] (). For complex κ(2)-N,O, an equilibrium results with free PPh3 giving the κ(1)-O complex [Rh{κ(1)-O-N(Dipp)C(O)C6F5}(PPh3)3] (). Heating a tol-d8 solution of E/Z-, , or / results in 2,6-diisopropylphenylisocyanate extrusion providing the corresponding [Rh]-C6F5 complex in good yield.
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