dc.contributor.author | McDonald, Aidan | |
dc.contributor.author | McManus, Caitlín | |
dc.contributor.author | Mondal, Prasenjit | |
dc.contributor.author | Lovisari, Marta | |
dc.contributor.author | Twamley, Brendan | |
dc.date.accessioned | 2019-12-12T15:15:40Z | |
dc.date.available | 2019-12-12T15:15:40Z | |
dc.date.issued | 2019 | |
dc.date.submitted | 2019 | en |
dc.identifier.citation | McManus, C., Mondal, P., Lovisari, M., Twamley, B. & McDonald, A.R., Carboxamidate Ligand Noninnocence in Proton Coupled Electron Transfer, Inorganic Chemistry, 58, 17, 2019, 4515-4523 | en |
dc.identifier.other | Y | |
dc.identifier.uri | https://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00055 | |
dc.identifier.uri | http://hdl.handle.net/2262/91072 | |
dc.description | PUBLISHED | en |
dc.description.abstract | Recent breakthroughs have brought into question the innocence (or not) of carboxamidate donor ligands in the reactivity of high-valent oxidants. To test the reactivity properties of high-valent carboxamidate complexes, [NiII(tBu-terpy)(L)] (1, tBu-terpy = 4,4′,4′′-tri-tert-butyl-2,2′;6′,2″-terpyridine; L = N,N′-(2,6-dimethylphenyl)-2,6-pyridinedicarboxamidate) was prepared and converted to [NiIII(tBu-terpy)(L)]+ (2) using ceric ammonium nitrate. 2 was characterized using electronic absorption and electron paramagnetic resonance spectroscopies and electrospray ionization mass spectrometry. 2 was found to be a capable oxidant of phenols and through kinetic analysis was found to oxidize these substrates via a nonconcerted or partially concerted proton coupled electron transfer (PCET) mechanism. The products of PCET oxidation of phenols by 2 were phenoxyl radical and the protonated form of 1, 1H+. 1H+ was crystallographically characterized providing convincing evidence of 1’s ability to act as a proton acceptor. We demonstrate that the complex remained intact through a full cycle of oxidation of 1 to 2, PCET of 2 to yield 1H+, and deprotonation of 1H+ to yield 1 followed by reoxidation of 1 to yield 2. The N–H bond dissociation energy of the protonated amide in 1H+ was determined to be 84 kcal/mol. Our findings illuminate the role carboxamidate ligands can play in PCET oxidation. | en |
dc.format.extent | 4515-4523 | en |
dc.language.iso | en | en |
dc.relation.ispartofseries | Inorganic Chemistry; | |
dc.relation.ispartofseries | 58; | |
dc.relation.ispartofseries | 17; | |
dc.rights | Y | en |
dc.subject | Carboxamidate ligands | en |
dc.subject | Proton coupled electron transfer (PCET) mechanism | en |
dc.title | Carboxamidate Ligand Noninnocence in Proton Coupled Electron Transfer | en |
dc.type | Journal Article | en |
dc.type.supercollection | scholarly_publications | en |
dc.type.supercollection | refereed_publications | en |
dc.identifier.peoplefinderurl | http://people.tcd.ie/aimcdona | |
dc.identifier.rssinternalid | 202400 | |
dc.identifier.doi | https://doi.org/10.1021/acs.inorgchem.9b00055 | |
dc.rights.ecaccessrights | openAccess | |
dc.identifier.orcid_id | 0000-0002-8930-3256 | |
dc.contributor.sponsor | Science Foundation Ireland (SFI) | en |
dc.contributor.sponsorGrantNumber | SFI/15/RS-URF/3307 | en |