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Ortho-aryl substituted DPEphos ligands: rhodium complexes featuring C–H anagostic interactions and B–H agostic bonds
The synthesis of new Schrock–Osborn Rh(i) pre-catalysts with ortho-substituted DPEphos ligands, [Rh(DPEphos-R)(NBD)][BAr(F)(4)] [R = Me, OMe, (i)Pr; Ar(F) = 3,5-(CF(3))(2)C(6)H(3)], is described. Along with the previously reported R = H variant, variable temperature (1)H NMR spectroscopic and single...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8246285/ https://www.ncbi.nlm.nih.gov/pubmed/34257884 http://dx.doi.org/10.1039/d1sc01430g |
Sumario: | The synthesis of new Schrock–Osborn Rh(i) pre-catalysts with ortho-substituted DPEphos ligands, [Rh(DPEphos-R)(NBD)][BAr(F)(4)] [R = Me, OMe, (i)Pr; Ar(F) = 3,5-(CF(3))(2)C(6)H(3)], is described. Along with the previously reported R = H variant, variable temperature (1)H NMR spectroscopic and single-crystal X-ray diffraction studies show that these all have axial (C–H)⋯Rh anagostic interactions relative to the d(8) pseudo square planar metal centres, that also result in corresponding downfield chemical shifts. Analysis by NBO, QTAIM and NCI methods shows these to be only very weak C–H⋯Rh bonding interactions, the magnitudes of which do not correlate with the observed chemical shifts. Instead, as informed by Scherer's approach, it is the topological positioning of the C–H bond with regard to the metal centre that is important. For [Rh(DPEphos–(i)Pr)(NBD)][BAr(F)(4)] addition of H(2) results in a Rh(iii) (i)Pr–C–H activated product, [Rh(κ(3),σ-P,O,P-DPEphos-(i)Pr′)(H)][BAr(F)(4)]. This undergoes H/D exchange with D(2) at the (i)Pr groups, reacts with CO or NBD to return Rh(i) products, and reaction with H(3)B·NMe(3)/tert-butylethene results in a dehydrogenative borylation to form a complex that shows both a non-classical B–H⋯Rh 3c-2e agostic bond and a C–H⋯Rh anagostic interaction at the same metal centre. |
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