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Isocyanate deinsertion from [small kappa]1-O amidates: facile access to perfluoroaryl rhodium(i) complexes

TitleIsocyanate deinsertion from [small kappa]1-O amidates: facile access to perfluoroaryl rhodium(i) complexes
Publication TypeJournal Article
Year of Publication2015
AuthorsDrover, MW, Schafer, LL, Love, JA
JournalDalton Trans.
Pagination-
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 [Rh2{[small mu ]2-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{[small kappa]1-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 [small kappa]1-O complex [Rh{[small kappa]1-O-N(Dipp)C(O)C6F5}(CNXyl)3] (6) while use of 3 equiv. of PPh3 provides the [small kappa]2-complex [Rh{[small kappa]2-N{,}O-N(Dipp)C(O)C6F5}(PPh3)2] (8). For complex [small kappa]2-N{,}O 8{,} an equilibrium results with free PPh3 giving the [small kappa]1-O complex [Rh{[small kappa]1-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.

URLhttp://dx.doi.org/10.1039/C5DT01981H
DOI10.1039/C5DT01981H