Synthesis, Isolation, and Characterization of Two Cationic Organobismuth(II) Pincer Complexes Relevant in Radical Redox Chemistry

Yang, Xiuxiu; Reijerse, Edward J.; Nöthling, Nils; SantaLucia, Daniel J.; Leutzsch, Markus; Schnegg, Alexander; Cornellà, Josep

doi:10.1021/jacs.2c12564

Cited by 19 publications

(13 citation statements)

References 45 publications

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“…The magnetic moment linearly decreases with decreasing temperature and shows a value of 1.98 μ B at 300 K, which is comparable to reported Bi II radical compounds. 49,50,53 The latter value is consistent with a single unpaired electron S = 1/ 2 system.…”

Section: Synthesis and Characterization Of Monoatomic Bi I Complexes ...supporting

confidence: 69%

“…The unequivocal identification of Bi II radical complexes is challenging, in particular, the electron paramagnetic resonance (EPR) characterization due to the enormous (isotropic and anisotropic) hyperfine interactions and the large nuclear quadrupole moment of the 209 Bi nucleus ( I = 9/2; 100% natural abundance). Until now, only a few stable monatomic Bi II radicals have been reported (Chart b,c). − Among these, C 48 is considered a redox radical Bi II /Bi III couple and lacks observable EPR signals. Compounds D 49 and E , are isolable neutral Bi II radicals with the unpaired electron predominantly residing at the Bi atom.…”

Section: Introductionmentioning

confidence: 99%

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Stabilizing Monoatomic Two-Coordinate Bismuth(I) and Bismuth(II) Using a Redox Noninnocent Bis(germylene) Ligand

Xu,

Pan,

Yao

et al. 2024

J. Am. Chem. Soc.

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The formation of isolable monatomic Bi I complexes and Bi II radical species is challenging due to the pronounced reducing nature of metallic bismuth. Here, we report a convenient strategy to tame Bi I and Bi II atoms by taking advantage of the redox noninnocent character of a new chelating bis(germylene) ligand. The remarkably stable novel Bi I cation complex 4, supported by the new bis(iminophosphonamido-germylene)xanthene ligand [(P)Ge II (Xant)Ge II (P)] 1, [(P)Ge II (Xant)Ge II (P) = Ph 2 P-(NtBu) 2 Ge II (Xant)Ge II (NtBu) 2 PPh 2 , Xant = 9,9-dimethyl-xanthene-4,5-diyl], was synthesized by a two-electron reduction of the cationic Bi III I 2 precursor complex 3 with cobaltocene (Cp 2 Co) in a molar ratio of 1:2. Notably, owing to the redox noninnocent character of the germylene moieties, the positive charge of Bi I cation 4 migrates to one of the Ge atoms in the bis(germylene) ligand, giving rise to a germylium(germylene) Bi I complex as suggested by DFT calculations and X-ray photoelectron spectroscopy (XPS). Likewise, migration of the positive charge of the Bi III I 2 cation of 3 results in a bis(germylium)Bi III I 2 complex. The delocalization of the positive charge in the ligand engenders a much higher stability of the Bi I cation 4 in comparison to an isoelectronic two-coordinate Pb 0 analogue (plumbylone; decomposition below −30 °C). Interestingly, 4[BAr F ] undergoes a reversible single-electron transfer (SET) reaction (oxidation) to afford the isolable Bi II radical complex 5 in 5[BAr F ] 2 . According to electron paramagnetic resonance (EPR) spectroscopy, the unpaired electron predominantly resides at the Bi II atom. Extending the redox reactivity of 4[OTf] employing AgOTf and MeOTf affords Bi III (OTf) 2 complex 7 and Bi III Me complex 8, respectively, demonstrating the high nucleophilic character of Bi I cation 4.

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Section: Synthesis and Characterization Of Monoatomic Bi I Complexes ...supporting

confidence: 69%

Section: Introductionmentioning

confidence: 99%

Stabilizing Monoatomic Two-Coordinate Bismuth(I) and Bismuth(II) Using a Redox Noninnocent Bis(germylene) Ligand

Xu,

Pan,

Yao

et al. 2024

J. Am. Chem. Soc.

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“…[93] In 2023, Cornella and co-workers reported the synthesis and characterization of stable Bi(II) radical cations generated by single-electron oxidation of N,C,N-Bi(I) complexes (Scheme 16). [94] Treatment of bismuthinidenes 68 with 1 equiv. of ferrocenium cation allowed the isolation of Bi(II) radical cations 69.…”

Section: Generation By Oxidation Of Bi(i)mentioning

confidence: 99%

Bismuth in Radical Chemistry and Catalysis

Mato,

Cornella

2023

Angew Chem Int Ed

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Whereas indications of radical reactivity in bismuth compounds can be traced back to the 19th century, the preparation and characterization of both transient and persistent bismuth‐radical species has only been established in recent decades. These advancements led to the emergence of the field of bismuth radical chemistry, mirroring the progress seen for other main‐group elements. The seminal and fundamental studies in this area have ultimately paved the way for the development of catalytic methodologies involving bismuth‐radical intermediates, a promising approach that remains largely untapped in the broad landscape of synthetic organic chemistry. In this review, we delve into the milestones that eventually led to the present state‐of‐the‐art in the field of radical bismuth chemistry. Our focus aims at outlining the intrinsic discoveries in fundamental inorganic/organometallic chemistry and contextualizing their practical applications in organic synthesis and catalysis.

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“…[23][24][25] Only very recently, Schulz and Cornella reported the preparation and in some cases full characterization of the first mononuclear cationic organobismuth(II) compounds bearing either a cyclic alkyl amino carbene (cAAC) or an N,C,N pincer ligand framework, providing benchmark experimental and theoretical studies of such species (Scheme 3). 26,27 In particular, compounds 10 and 11 were obtained by oxidation of the Bi(I)-precursors 8 and 9 with ferrocenium salts. A combination of NMR and EPR spectroscopy as well as SQUID magnetometry provided strong evidence to identify 10 and 11 as paramagnetic S = 1/2 compounds.…”

Section: Introductionmentioning

confidence: 99%

Bismuth-Centered Radical Species: Access and Applications in Organic Synthesis

Lichtenberg,

Martínez

2023

Synlett

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Recent advances in the isolation of tamed Bismuth radicals and the selective in-situ-generation of highly reactive Bismuth radicals have set the stage for the application of these compounds in organic and organometallic synthesis and catalysis. Here, we provide a summary of the strategies that have been developed to access and exploit Bismuth-centered radical species. Important strategies for accessing Bismuth radical species are presented and and key examples of their applications in organic synthesis are outlined, highlighting how this class of compounds has emerged as new set of valuable tools for synthetic practitioners.

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Synthesis, Isolation, and Characterization of Two Cationic Organobismuth(II) Pincer Complexes Relevant in Radical Redox Chemistry

Cited by 19 publications

References 45 publications

Stabilizing Monoatomic Two-Coordinate Bismuth(I) and Bismuth(II) Using a Redox Noninnocent Bis(germylene) Ligand

Stabilizing Monoatomic Two-Coordinate Bismuth(I) and Bismuth(II) Using a Redox Noninnocent Bis(germylene) Ligand

Bismuth in Radical Chemistry and Catalysis

Bismuth-Centered Radical Species: Access and Applications in Organic Synthesis

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Synthesis, Isolation, and Characterization of Two Cationic Organobismuth(II) Pincer Complexes Relevant in Radical Redox Chemistry

Cited by 19 publications

References 45 publications

Stabilizing Monoatomic Two-Coordinate Bismuth(I) and Bismuth(II) Using a Redox Noninnocent Bis(germylene) Ligand

Stabilizing Monoatomic Two-Coordinate Bismuth(I) and Bismuth(II) Using a Redox Noninnocent Bis(germylene) Ligand

Bismuth in Radical Chemistry and Catalysis

Bismuth-Centered Radical Species: Access and Applications in ­Organic Synthesis

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Bismuth-Centered Radical Species: Access and Applications in Organic Synthesis