Abstract
Reaction of the amidate ligand salts Na[N(Dipp)C(O)R] (R = Ph (1a), tBu (1b); Dipp = 2,6-diisopropylphenyl) with [Rh(NBD)Cl]2 (NBD = norbornadiene) proceeds to give the dirhodium(I) complexes [Rh2{μ2-N,O-N(Dipp)C(O)R}2(NBD)2] (R = Ph (2a), tBu (2b)) with variable coordination behavior. For complex 2b, a monomer–dimer equilibrium with the mononuclear complex [Rh{κ2-N,O-N(Dipp)C(O)tBu}(NBD)] (3b) was established for the first time. Precursors 2a,b were treated with PPh3 and PCy3, giving the distorted-square-planar κ2-N,O amidates [Rh{κ2-N,O-N(Dipp)C(O)R}(PPh3)2] (R = Ph (4a), tBu (4b)) or the κ1-O complexes [Rh{κ1-O-N(Dipp)C(O)R}(NBD)(PCy3)] (R = Ph (5a), tBu (5b)). Initial reactivity screening showed that complex 4b undergoes O2 activation, providing Ph3P═O; via the transient peroxo complex 6b, which was characterized in the solution phase. The κ2-N,O amidate coordination in 6b has been conclusively established by diagnostic 13C{1H} NMR spectroscopy.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
