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Single-crystal to cingle-crystal addition of H2to [Ir(iPr-PONOP)(propene)][BArF4] and comparison between solid-state and solution reactivity
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dc.contributor.author | Royle, Cameron G. | |
dc.contributor.author | Sotorrios, Lia | |
dc.contributor.author | Gyton, Matthew R. | |
dc.contributor.author | Brodie, Claire N. | |
dc.contributor.author | Burnage, Arron L. | |
dc.contributor.author | Furfari, Samantha K. | |
dc.contributor.author | Marini, Anna | |
dc.contributor.author | Warren, Mark R. | |
dc.contributor.author | Macgregor, Stuart A. | |
dc.contributor.author | Weller, Andrew S. | |
dc.date.accessioned | 2024-05-15T14:30:09Z | |
dc.date.available | 2024-05-15T14:30:09Z | |
dc.date.issued | 2022-11-28 | |
dc.identifier | 300485261 | |
dc.identifier | 1881250e-3f64-4e8e-8713-e888c0215184 | |
dc.identifier | 85135891738 | |
dc.identifier.citation | Royle , C G , Sotorrios , L , Gyton , M R , Brodie , C N , Burnage , A L , Furfari , S K , Marini , A , Warren , M R , Macgregor , S A & Weller , A S 2022 , ' Single-crystal to cingle-crystal addition of H 2 to [Ir( i Pr-PONOP)(propene)][BAr F 4 ] and comparison between solid-state and solution reactivity ' , Organometallics , vol. 41 , no. 22 , pp. 3270-3280 . https://doi.org/10.1021/acs.organomet.2c00274 | en |
dc.identifier.issn | 0276-7333 | |
dc.identifier.other | ORCID: /0000-0003-3454-6776/work/156626211 | |
dc.identifier.uri | https://hdl.handle.net/10023/29888 | |
dc.description | The EPSRC (EP/M024210/2, EP/T019867/1), SCG Chemicals, The Clarendon Trust, The Leverhulme Trust (RPG-2020-184), Diamond Light Source for funding (PhD studentship to AM). | en |
dc.description.abstract | The reactivity of the Ir(I) PONOP pincer complex [Ir(iPr-PONOP)(η2-propene)][BArF4], 6, [iPr-PONOP = 2,6-(iPr2PO)2C6H3N, ArF= 3,5-(CF3)2C6H3] 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 H2and propene, and then the application of vacuum, to [Ir(iPr-PONOP)(η2-COD)][BArF4], 1, a reaction manifold that proceeds via the Ir(III) dihydrogen/dihydride complex [Ir(iPr-PONOP)(H2)H2][BArF4], 2, and the Ir(III) dihydride propene complex [Ir(iPr-PONOP)(η2-propene)H2][BArF4], 7, respectively. In solution (CD2Cl2) 6 undergoes rapid reaction with H2to 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 H2in an SC-SC reaction, but unlike in solution the onward reaction (i.e., insertion) does not occur, as confirmed by labeling studies using D2. The solid-state structure of 7 reveals that, on addition of H2to 6, the PONOP ligand moves by 90° within a cavity of [BArF4]-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. H2addition 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(iPr-PONOP)H2(η1-H3B·NMe3)][BArF4], 5, is also reported as part of these studies. | |
dc.format.extent | 11 | |
dc.format.extent | 2836582 | |
dc.language.iso | eng | |
dc.relation.ispartof | Organometallics | en |
dc.subject | Physical and Theoretical Chemistry | en |
dc.subject | Organic Chemistry | en |
dc.subject | Inorganic Chemistry | en |
dc.subject | DAS | en |
dc.subject | AC | en |
dc.title | Single-crystal to cingle-crystal addition of H2to [Ir(iPr-PONOP)(propene)][BArF4] and comparison between solid-state and solution reactivity | en |
dc.type | Journal article | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.identifier.doi | 10.1021/acs.organomet.2c00274 | |
dc.description.status | Peer reviewed | en |
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