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Issue 45, 2015
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Isocyanate deinsertion from κ1-O amidates: facile access to perfluoroaryl rhodium(i) complexes

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Abstract

Reaction of the amidate ligand salt, Na[N(Dipp)C(O)C6F5] (1) (Dipp = 2,6-diisopropylphenyl) with [Rh(NBD)Cl]2 (NBD = norbornadiene) results in formation of the dirhodium(I) complex [Rh22-N,O-N(Dipp)C(O)C6F5}2(NBD)2] (2). Reaction of 2 with PCy3 at room temperature provides an equilibrium mixture of the geometric isomers (E/Z)-[Rh{κ1-O-N(Dipp)C(O)C6F5}(NBD)(PCy3)] (E/Z-3). Treatment of 2 with 3 equiv. of CNXyl (Xyl = 2,6-dimethylphenyl) gives the κ1-O complex [Rh{κ1-O-N(Dipp)C(O)C6F5}(CNXyl)3] (6) while use of 3 equiv. of PPh3 provides the κ2-complex [Rh{κ2-N,O-N(Dipp)C(O)C6F5}(PPh3)2] (8). For complex κ2-N,O8, an equilibrium results with free PPh3 giving the κ1-O complex [Rh{κ1-O-N(Dipp)C(O)C6F5}(PPh3)3] (9). Heating a tol-d8 solution of E/Z-3, 6, or 8/9 results in 2,6-diisopropylphenylisocyanate extrusion providing the corresponding [Rh]-C6F5 complex in good yield.

Graphical abstract: Isocyanate deinsertion from κ1-O amidates: facile access to perfluoroaryl rhodium(i) complexes

  • This article is part of the themed collection: Fluorine
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Publication details

The article was received on 26 May 2015, accepted on 29 Jul 2015 and first published on 10 Aug 2015


Article type: Paper
DOI: 10.1039/C5DT01981H
Dalton Trans., 2015,44, 19487-19493

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    Isocyanate deinsertion from κ1-O amidates: facile access to perfluoroaryl rhodium(I) complexes

    M. W. Drover, L. L. Schafer and J. A. Love, Dalton Trans., 2015, 44, 19487
    DOI: 10.1039/C5DT01981H

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