Sequential X-ray-Induced Single-Crystal to Single-Crystal Transformation followed by Topotactic Reduction in a Potassium Crown Ether Complex of Tetrachloroaurate(III)

Sethi, Navpreet K.; Whitwood, Adrian C.; Bruce, Duncan W.

doi:10.1021/acs.inorgchem.8b02130

Cited by 3 publications

(2 citation statements)

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“…The addition of H 2 to 6 to form 7 also results in a change in the oxidation state of the metal, accompanied by a move from pseudo square planar to octahedral. SC-SC transformations that involve an overall change in oxidation state have been reported previously, for example, Mn(II)/Mn(IV); Co(II)/Co(III); Rh(I)/Rh(III); ,, Ir(I)/Ir(III); Ir(III)/Ir(V); and Au(I)/Au(III) …”

Section: Resultssupporting

confidence: 55%

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Single-Crystal to Single-Crystal Addition of H₂ to [Ir(ⁱPr-PONOP)(propene)][BAr^F₄] and Comparison Between Solid-State and Solution Reactivity

et al. 2022

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The reactivity of the Ir(I) PONOP pincer complex [Ir( i Pr-PONOP)(η 2 -propene)][BAr F 4 ], 6, [ i Pr-PONOP = 2,6-( i Pr 2 PO) 2 C 6 H 3 N, Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ] was studied in solution and the solid state, both experimentally, using molecular density functional theory (DFT) and periodic-DFT computational methods, as well as in situ single-crystal to single-crystal (SC-SC) techniques. Complex 6 is synthesized in solution from sequential addition of H 2 and propene, and then the application of vacuum, to [Ir( i Pr-PONOP)(η 2 -COD)][BAr F 4 ], 1, a reaction manifold that proceeds via the Ir(III, 2, and the Ir(III) dihydride propene complex [Ir( i Pr-PONOP)(η 2 -propene)H 2 ][BAr F 4 ], 7, respectively. In solution (CD 2 Cl 2 ) 6 undergoes rapid reaction with H 2 to form dihydride 7 and then a slow (3 d) onward reaction to give dihydrogen/dihydride 2 and propane. DFT calculations on the molecular cation in solution support this slow, but productive, reaction, with a calculated barrier to rate-limiting propene migratory insertion of 24.8 kcal/mol. In the solid state single-crystals of 6 also form complex 7 on addition of H 2 in an SC-SC reaction, but unlike in solution the onward reaction (i.e., insertion) does not occur, as confirmed by labeling studies using D 2 . The solid-state structure of 7 reveals that, on addition of H 2 to 6, the PONOP ligand moves by 90°within a cavity of [BAr F 4 ] − anions rather than the alkene moving. Periodic DFT calculations support the higher barrier to insertion in the solid state (ΔG ‡ = 26.0 kcal/mol), demonstrating that the single-crystal environment gates onward reactivity compared to solution. H 2 addition to 6 to form 7 is reversible in both solution and the solid state, but in the latter crystallinity is lost. A rare example of a sigma amine-borane pincer complex, [Ir( i Pr-PONOP)H 2 (η 1 -H 3 B•NMe 3 )][BAr F 4 ], 5, is also reported as part of these studies.

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Section: Resultssupporting

confidence: 55%

“…SC-SC transformations that involve an overall change in oxidation state have been reported previously, 10 for example, Mn(II)/Mn(IV); 60 Co(II)/Co(III); 61 Rh(I)/Rh(III); 13 , 62 , 63 Ir(I)/Ir(III); 21 Ir(III)/Ir(V); 64 and Au(I)/Au(III). 65 …”

Section: Resultsmentioning

confidence: 99%

Single-Crystal to Single-Crystal Addition of H₂ to [Ir(ⁱPr-PONOP)(propene)][BAr^F₄] and Comparison Between Solid-State and Solution Reactivity

et al. 2022

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A Gold(I)–Acetylene Complex Synthesised using Single‐Crystal Reactivity

Johnson,

Storm,

Sajjad

et al. 2024

Angewandte Chemie

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Using single‐crystal to single‐crystal solid/gas reactivity the gold(I) acetylene complex [Au(L1)(η2‐HC≡CH)][BArF4] is cleanly synthesized by addition of acetylene gas to single crystals of [Au(L1)(CO)][BArF4] [L1 = tris‐2‐(4,4’‐di‐tert‐butylbiphenyl)phosphine, ArF = 3,5‐(CF3)2C6H3]. This simplest gold‐alkyne complex has been characterized by single crystal X‐ray diffraction, solution and solid‐state NMR spectroscopy and periodic DFT. Bonding of HC≡CH with [Au(L1)]+ comprises both σ‐donation and π‐backdonation with additional dispersion interactions within the cavity‐shaped phosphine.

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A Gold(I)–Acetylene Complex Synthesised using Single‐Crystal Reactivity

Johnson,

Storm,

Sajjad

et al. 2024

Angew Chem Int Ed

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Sequential X-ray-Induced Single-Crystal to Single-Crystal Transformation followed by Topotactic Reduction in a Potassium Crown Ether Complex of Tetrachloroaurate(III)

Cited by 3 publications

References 20 publications

Single-Crystal to Single-Crystal Addition of H₂ to [Ir(ⁱPr-PONOP)(propene)][BAr^F₄] and Comparison Between Solid-State and Solution Reactivity

Single-Crystal to Single-Crystal Addition of H₂ to [Ir(ⁱPr-PONOP)(propene)][BAr^F₄] and Comparison Between Solid-State and Solution Reactivity

A Gold(I)–Acetylene Complex Synthesised using Single‐Crystal Reactivity

A Gold(I)–Acetylene Complex Synthesised using Single‐Crystal Reactivity

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Sequential X-ray-Induced Single-Crystal to Single-Crystal Transformation followed by Topotactic Reduction in a Potassium Crown Ether Complex of Tetrachloroaurate(III)

Cited by 3 publications

References 20 publications

Single-Crystal to Single-Crystal Addition of H2 to [Ir(iPr-PONOP)(propene)][BArF4] and Comparison Between Solid-State and Solution Reactivity

Single-Crystal to Single-Crystal Addition of H2 to [Ir(iPr-PONOP)(propene)][BArF4] and Comparison Between Solid-State and Solution Reactivity

A Gold(I)–Acetylene Complex Synthesised using Single‐Crystal Reactivity

A Gold(I)–Acetylene Complex Synthesised using Single‐Crystal Reactivity

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Product

Resources

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Single-Crystal to Single-Crystal Addition of H₂ to [Ir(ⁱPr-PONOP)(propene)][BAr^F₄] and Comparison Between Solid-State and Solution Reactivity

Single-Crystal to Single-Crystal Addition of H₂ to [Ir(ⁱPr-PONOP)(propene)][BAr^F₄] and Comparison Between Solid-State and Solution Reactivity