biostudies-literatureHood TMEuropean Research CouncilRoyal Society7593-7601https://www.ebi.ac.uk/biostudies/studies/S-EPMC6549213biostudies-literatureUnknown58(11)The synthesis and characterization of a homologous series of five-coordinate rhodium(III) and iridium(III) complexes of PNP (2,6-( tBu₂PCH₂)₂C₅H₃N) and PONOP (2,6-( tBu₂PO)₂C₅H₃N) pincer ligands are described: [M(PNP)(biph)][BAr^F₄] (M = Rh, 1a; Ir, 1b; biph = 2,2'-biphenyl; Ar^F = 3,5-(CF₃)₂C₆H₃) and [M(PONOP)(biph)][BAr^F₄] (M = Rh, 2a; Ir, 2b). These complexes are structurally dynamic in solution, exhibiting pseudorotation of the biph ligand on the ¹H NMR time scale (Δ G^⧧ ca. 60 kJ mol^-1) and, in the case of the flexible PNP complexes, undergoing interconversion between helical and puckered pincer ligand conformations (Δ G^⧧ ca. 10 kJ mol^-1). Remarkably, the latter is sufficiently facile that it persists in the solid state, leading to temperature-dependent disorder in the associated X-ray crystal structures. Reaction of 1 and 2 with CO occurs for the iridium congeners 1b and 2b, leading to the formation of sterically congested carbonyl derivatives.Inorganic chemistrySynthesis and Structural Dynamics of Five-Coordinate Rh(III) and Ir(III) PNP and PONOP Pincer Complexes.PMC6549213637313UF100592UF150675Gyton MRChaplin ABHood TMLeforestier BfalseSynthesis and Structural Dynamics of Five-Coordinate Rh(III) and Ir(III) PNP and PONOP Pincer Complexes.The synthesis and characterization of a homologous series of five-coordinate rhodium(III) and iridium(III) complexes of PNP (2,6-( tBu₂PCH₂)₂C₅H₃N) and PONOP (2,6-( tBu₂PO)₂C₅H₃N) pincer ligands are described: [M(PNP)(biph)][BAr^F₄] (M = Rh, 1a; Ir, 1b; biph = 2,2'-biphenyl; Ar^F = 3,5-(CF₃)₂C₆H₃) and [M(PONOP)(biph)][BAr^F₄] (M = Rh, 2a; Ir, 2b). These complexes are structurally dynamic in solution, exhibiting pseudorotation of the biph ligand on the ¹H NMR time scale (Δ G^⧧ ca. 60 kJ mol^-1) and, in the case of the flexible PNP complexes, undergoing interconversion between helical and puckered pincer ligand conformations (Δ G^⧧ ca. 10 kJ mol^-1). Remarkably, the latter is sufficiently facile that it persists in the solid state, leading to temperature-dependent disorder in the associated X-ray crystal structures. Reaction of 1 and 2 with CO occurs for the iridium congeners 1b and 2b, leading to the formation of sterically congested carbonyl derivatives.2019-01-01T00:00:00Z2019 Jun2024-12-03T18:15:05.329Z2019-07-24T07:09:59ZS-EPMC65492133111763410.1021/acs.inorgchem.9b00957