dc.contributor.author
Xu, Jian
dc.contributor.author
Pan, Sudip
dc.contributor.author
Yao, Shenglai
dc.contributor.author
Lorent, Christian
dc.contributor.author
Teutloff, Christian
dc.contributor.author
Zhang, Zhaoyin
dc.contributor.author
Fan, Jun
dc.contributor.author
Molino, Andrew
dc.contributor.author
Krause, Konstantin B.
dc.contributor.author
Bittl, Robert
dc.date.accessioned
2024-04-16T10:45:18Z
dc.date.available
2024-04-16T10:45:18Z
dc.identifier.uri
https://refubium.fu-berlin.de/handle/fub188/43257
dc.identifier.uri
http://dx.doi.org/10.17169/refubium-42973
dc.description.abstract
The formation of isolable monatomic BiI complexes and BiII radical species is challenging due to the pronounced reducing nature of metallic bismuth. Here, we report a convenient strategy to tame BiI and BiII atoms by taking advantage of the redox noninnocent character of a new chelating bis(germylene) ligand. The remarkably stable novel BiI cation complex 4, supported by the new bis(iminophosphonamido-germylene)xanthene ligand [(P)GeII(Xant)GeII(P)] 1, [(P)GeII(Xant)GeII(P) = Ph2P(NtBu)2GeII(Xant)GeII(NtBu)2PPh2, Xant = 9,9-dimethyl-xanthene-4,5-diyl], was synthesized by a two-electron reduction of the cationic BiIIII2 precursor complex 3 with cobaltocene (Cp2Co) in a molar ratio of 1:2. Notably, owing to the redox noninnocent character of the germylene moieties, the positive charge of BiI cation 4 migrates to one of the Ge atoms in the bis(germylene) ligand, giving rise to a germylium(germylene) BiI complex as suggested by DFT calculations and X-ray photoelectron spectroscopy (XPS). Likewise, migration of the positive charge of the BiIIII2 cation of 3 results in a bis(germylium)BiIIII2 complex. The delocalization of the positive charge in the ligand engenders a much higher stability of the BiI cation 4 in comparison to an isoelectronic two-coordinate Pb0 analogue (plumbylone; decomposition below −30 °C). Interestingly, 4[BArF] undergoes a reversible single-electron transfer (SET) reaction (oxidation) to afford the isolable BiII radical complex 5 in 5[BArF]2. According to electron paramagnetic resonance (EPR) spectroscopy, the unpaired electron predominantly resides at the BiII atom. Extending the redox reactivity of 4[OTf] employing AgOTf and MeOTf affords BiIII(OTf)2 complex 7 and BiIIIMe complex 8, respectively, demonstrating the high nucleophilic character of BiI cation 4.
en
dc.format.extent
12 Seiten
dc.rights.uri
https://creativecommons.org/licenses/by/4.0/
dc.subject
Electron paramagnetic resonance spectroscopy
en
dc.subject.ddc
500 Naturwissenschaften und Mathematik::540 Chemie::540 Chemie und zugeordnete Wissenschaften
dc.title
Stabilizing Monoatomic Two-Coordinate Bismuth(I) and Bismuth(II) Using a Redox Noninnocent Bis(germylene) Ligand
dc.type
Wissenschaftlicher Artikel
dcterms.bibliographicCitation.doi
10.1021/jacs.3c13016
dcterms.bibliographicCitation.journaltitle
Journal of the American Chemical Society
dcterms.bibliographicCitation.number
9
dcterms.bibliographicCitation.pagestart
6025
dcterms.bibliographicCitation.pageend
6036
dcterms.bibliographicCitation.volume
146
dcterms.bibliographicCitation.url
https://doi.org/10.1021/jacs.3c13016
refubium.affiliation
Physik
refubium.resourceType.isindependentpub
no
dcterms.accessRights.openaire
open access
dcterms.isPartOf.eissn
1520-5126
refubium.resourceType.provider
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