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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.

Ortho-aryl substituted DPEphos ligands: rhodium complexes featuring C–H anagostic interactions and B–H agostic bonds