Mild activation of Ir Cl bond upon the interaction of pincer iridium hydride (BuPCP)IrH(Cl) with acids and bases

Titova, Ekaterina M.; Osipova, Elena S.; Gulyaeva, Ekaterina S.; Torocheshnikov, V. N.; Pavlov, A. A.; Silantyev, Gleb A.; Filippov, Oleg A.; Shubina, Elena S.; Belkova, Natalia V.

doi:10.1016/j.jorganchem.2016.11.010

Cited by 8 publications

(14 citation statements)

References 39 publications

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“…The molecular electrostatic potential (MEP) minima, V S, min , are also located on the Cl ligand in complexes 1 , 4 – 10 and possess two extrema points (Figure ), which correspond to the two occupied p‐orbitals. This is in good agreement with the experimentally observed hydrogen bonding of alcohols and –NH 2 to chloride , . The introduction of COOMe and NO 2 substituents (complexes 3 , 7 , 8 ) expectedly decreases the chloride basicity (see V S, min in Table ), and the global MEP minima in these complexes are located on the substituents′ oxygen atoms.…”

Section: Resultssupporting

confidence: 88%

Effect of Ligands on the Lewis Acidity of the Metal and the Binding of N‐Bases to Iridium Pincer Complexes

et al. 2019

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The coordination of pyridine (Py) and benzonitrile (PhCN) to benzene based pincer hydridochlorides [(PCP)IrH(Cl)] (1), [(POCOP)IrH(Cl)] (2), [{EtO(O)C‐POCOP}IrH(Cl)] (3), and [(PCN)IrH(Cl)] (4) was studied spectroscopically and computationally to deduce the ligand influence. The variable temperature NMR (1H, 31P, 15N) and UV/Visible spectroscopic measurements revealed preferential coordination of these N‐donor ligands in the apical position of 1–4 and gave the formation enthalpies for the hexacoordinate complexes, which follow the order: 1 ≈ 4 > 3 > 2. This order nicely agrees with the order of Lewis acidity obtained for these complexes in DFT calculations. The orbital and electron density distribution analysis were performed at the DFT/M06 theory level for 1–4 and a series of p‐substituted PCP‐based hydridochlorides. The increasing Lewis acidity of iridium [as a maximum energy, VS,max, of molecular electrostatic potential (MEP)] correlates with decreasing basicity of Cl‐ligand (as MEP minimum, VS,min) as well as with Hammett σp parameters of p‐substituents. Importantly, these properties are conserved upon conversion into the corresponding dihydrides, as shown on the example of 1 and 4.

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Section: Resultssupporting

confidence: 88%

Effect of Ligands on the Lewis Acidity of the Metal and the Binding of N‐Bases to Iridium Pincer Complexes

et al. 2019

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“…55(3)/157.51 (4)°for Ir 8,26 ). The C aryl −M−CO angles are, however, essentially the same across all three compounds (179.30 (8)°for Co, 178.80 (6)°for Rh, and 178.9(3)/179.47 (18)°for Ir). All bonds to the metal center are shorter for the Co-containing complex 1 than for the related Rh or Ir complexes, which is in line with the smaller covalent radius of Co. 27 Diamagnetic 1 is formally Co I and exhibits only one virtual triplet at 1.36 ppm for the t Bu protons in the 1 H NMR spectrum, indicating approximate C 2v symmetry in both the solution and solid state.…”

Section: ■ Results and Discussionmentioning

confidence: 89%

“…Removal of the CO atmosphere resulted in partial conversion back to ( tBu POCOP)Co(I). X-ray diffraction quality crystals were grown from a saturated benzene solution of 5 under an atmosphere of CO. ( tBu POCOP)Co(H) (6). ( tBu POCOP)Co(I) (60 mg, 0.10 mmol) was placed in a Teflon-lined, stainless steel Parr reactor with NaH (47 mg, 2.07 mmol), THF (5 mL), and a stir bar.…”

Section: ■ Conclusionmentioning

confidence: 99%

“…We thank Dr. Sophia D. T. Cherry for the kind gifts of ( tBu POCOP)Rh(CO) and ( iPr POCOP)Rh(CO) and Dr. Werner Kaminsky for the solution of the solid-state structure of ( tBu POCOP)Co(H) (6). This work was funded by the NSF (CHE-1361928).…”

Section: ■ Acknowledgmentsmentioning

confidence: 99%

“…Group 9 “pincer” complexes are ubiquitous in inorganic chemistry and have been studied extensively for a variety of reactions. − POCOP (POCOP = κ 3 -C 6 H 3 -1,3-[OPR 2 ] 2 , R = alkyl, aryl) is a commonly used subclass of these meridionally binding, chelating ligands and has been incorporated into frameworks such as (POCOP)M(CO) (where M = Ir, ,,, Rh − ), though direct Co analogues have remained elusive. Here we report the first example of a POCOP-supported four-coordinate monocarbonyl complex, ( tBu POCOP)Co(CO), which allows for direct comparison, in terms of both structure and reactivity, with its second- and third-row metal counterparts.…”

Section: Introductionmentioning

confidence: 99%

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