2021
DOI: 10.1002/anie.202101423
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Stimulation of Redox‐Induced Electron Transfer by Interligand Hydrogen Bonding in a Cobalt Complex with Redox‐Active Guanidine Ligand

Abstract: Octahedrally coordinated cobalt(II) complexes with ar edox-active bisguanidine ligand and acac co-ligands were synthesized and their redoxc hemistry analysed in detail. The N À Hfunctions in abisguanidine ligand with partially alkylated guanidino groups form N À H•••O hydrogen bonds with the acac co-ligands,t hereby massively influencing the redox chemistry. Fora ll complexes,t he first one-electron oxidation is metalcentred, leading to Co III complexes with neutral bisguanidine ligand units.Further one-electr… Show more

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Cited by 26 publications
(74 citation statements)
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“…The potentials ( E 1/2 values) for the first (one‐electron) redox processes in [Co(acac) 2 (L1)] and [Co(acac) 2 (L2)], E 1/2 =−0.56 V for [Co(acac) 2 (L1)] + /[Co(acac) 2 (L1)] and E 1/2 =−0.54 V for [Co(acac) 2 (L2)] + /[Co(acac) 2 (L2)], are lower than the potentials of the free ligands L1 and L2 ( E 1/2 =−0.25 V ( E ox =−0.19 V) for L1 ⋅ + /L1 0 and E 1/2 =−0.46 V ( E ox =−0.37 V) for L2 ⋅ + /L2 0 ), [36] clearly showing that they belong to metal‐centered redox events [43] . Consequently, one‐electron oxidation of the Co II complexes with acac co‐ligands leads to Co III complexes with radical monocationic bisguanidine ligand unit.…”
Section: Resultsmentioning
confidence: 96%
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“…The potentials ( E 1/2 values) for the first (one‐electron) redox processes in [Co(acac) 2 (L1)] and [Co(acac) 2 (L2)], E 1/2 =−0.56 V for [Co(acac) 2 (L1)] + /[Co(acac) 2 (L1)] and E 1/2 =−0.54 V for [Co(acac) 2 (L2)] + /[Co(acac) 2 (L2)], are lower than the potentials of the free ligands L1 and L2 ( E 1/2 =−0.25 V ( E ox =−0.19 V) for L1 ⋅ + /L1 0 and E 1/2 =−0.46 V ( E ox =−0.37 V) for L2 ⋅ + /L2 0 ), [36] clearly showing that they belong to metal‐centered redox events [43] . Consequently, one‐electron oxidation of the Co II complexes with acac co‐ligands leads to Co III complexes with radical monocationic bisguanidine ligand unit.…”
Section: Resultsmentioning
confidence: 96%
“…Consequently, [Co(hfacac) 2 (L1)](PF 6 ), [Co(hfacac) 2 (L2)](PF 6 ) and [Co(hfacac) 2 (L3)](PF 6 ) are high‐spin Co II complexes with radical monocationic guanidine ligand (summing up to four unpaired electrons). By contrast, one‐electron oxidation of the complexes with the acac co‐ligands was shown to be metal‐based, leading to diamagnetic Co III complexes with neutral guanidine ligand unit [43] . The second one‐electron oxidation leads to high‐spin Co II complexes with dicationic guanidine ligand (three unpaired electrons) for complexes with hfacac co‐ligands.…”
Section: Resultsmentioning
confidence: 98%
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“…Die [38] )e indeutig auf die Präsenz des dikationischen Liganden, L3 2+ ,h in, was auf das Vorhandensein eines Co II A ufgrund von kombinierten s-u nd p-Beiträgen zu der Metall-Guanidin-Bindung [47] steigen die N=C-Bindungslängen von 1.295-(1)/1.292(1) bzw.1 .293(2)/1.287(2) in den freien Liganden L1 und L2 [38] Tabelle 1: Ausgewählte Bindungslängen (in )fürstrukturell charakterisierte Komplexe [Co(acac) 2 (L1)] n+ (n = 0, 1o der 2) im Festkçrper. [48] Bindung 8 8]f ürdie strukturell charakterisierten Komplexe [Co(acac) 2 (L3)] n+ (n = 0o der 2) im Festkçrper. [48] Bindung/ Winkel [51] ist charakteristisch füro ktaedrische High-Spin-Co II -Komplexe.…”
Section: Ergebnisse Und Diskussionunclassified
“…[48] Bindung 8 8]f ürdie strukturell charakterisierten Komplexe [Co(acac) 2 (L3)] n+ (n = 0o der 2) im Festkçrper. [48] Bindung/ Winkel [51] ist charakteristisch füro ktaedrische High-Spin-Co II -Komplexe. [52,53]…”
Section: Ergebnisse Und Diskussionunclassified