Issue 45, 2015

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

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

Supplementary files

Article information

Article type
Paper
Submitted
26 พ.ค. 2558
Accepted
29 ก.ค. 2558
First published
10 ส.ค. 2558

Dalton Trans., 2015,44, 19487-19493

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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements