title: Isocyanate deinsertion from κ(1)-O amidates: facile access to perfluoroaryl rhodium(I) complexes.
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.
authors.affiliation: Department of Chemistry, The University of British Columbia, Vancouver, Canada. jenlove@chem.ubc.ca.
authors.forename: Marcus W
authors.initials: MW
authors.lastname: Drover
authors.affiliation: Department of Chemistry, The University of British Columbia, Vancouver, Canada. jenlove@chem.ubc.ca.
authors.forename: Laurel L
authors.initials: LL
authors.lastname: Schafer
authors.affiliation: Department of Chemistry, The University of British Columbia, Vancouver, Canada. jenlove@chem.ubc.ca.
authors.forename: Jennifer A
authors.initials: JA
authors.lastname: Love