A diarsene radical anion

Sieg, Grégoire; Fischer, Malte; Dankert, Fabian; Siewert, Jan‐Erik; Hering‐Junghans, Christian; Werncke, C. Gunnar

doi:10.1039/d2cc03237f

Cited by 4 publications

(6 citation statements)

References 37 publications

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“…The central As−As bond length of the radical anion 8 ⋅ − (2.3533(4) Å) is significantly elongated compared to the neutral diarsene 4 (2.2646(2) Å), but is still shorter than the sum of the covalent single bond radii (2.42 Å, Table 1). [41] Comparable results have been reported for diarsene ( V [14] ) and diphosphene radical anions, [47] respectively, indicating the population of the π* orbital of the As double bond by one electron as was confirmed by use of quantum chemical calculations (Figure 3). [48] The increase in negative charge is much more pronounced for the As 2 unit (−0.63 e) than for the Ga atoms (Σ −0.17 e) according to natural population analysis [49] .…”

Section: Resultssupporting

confidence: 68%

“…Diarsene ( V ), and dibismuthene ( II ) radical anions have only been recently structurally characterized, whereas the first distibene radical anion ( IV) was reported in 2006 (Scheme 1). [14,15] Dipnictenes radical anions possess a highly reductive nature and their reactivity is still hardly explored [11d,13,16] . In addition, radical cations of heavy dipnictenes are limited to diarsenes, which have been synthesized by single electron oxidation of NHC‐ ( VII ) and NHO‐coordinated ( VI ) diarsenes (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

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From Neutral Diarsenes to Diarsene Radical Ions and Diarsene Dications

Weinert,

Wölper,

Radović

et al. 2024

Chemistry A European J

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Diarsene [L(MeO)GaAs]2 (L = HC[C(Me)N(Ar)]2, Ar = 2,6iPr2C6H3, 4) reacts with MeOTf and MeNHC (MeNHC = 1,3,4,5‐tetramethylimidazol‐2‐ylidene) to the diarsene [L(TfO)GaAs]2 (5) and the carbene‐coordinated diarsene [L(MeO)GaAsAs(MeNHC)Ga(OMe)L] (6). The NHC‐coordination results in an inversion of the redox properties of the diarsene 4, which shows only a reversible reduction event at E1/2 = −2.06 V vs Fc0/+, whereas the carbene‐coordinated diarsene 6 shows a reversible oxidation event at E1/2 = −1.31 V vs Fc0/+1. Single electron transfer reactions of 4 and 6 yielded [K[2.2.2.]cryp][L(MeO)GaAs]2 (8) and [L(MeO)GaAsAs(MeNHC)Ga(OMe)L][B(C6F5)4] (9) containing the radical anion [L(MeO)GaAs]2•−

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Section: Resultssupporting

confidence: 68%

Section: Introductionmentioning

confidence: 99%

From Neutral Diarsenes to Diarsene Radical Ions and Diarsene Dications

Weinert,

Wölper,

Radović

et al. 2024

Chemistry A European J

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“…In agreement with these results 1 shows a reversible reduction at a half‐wave potential E 1/2 =−2.25 V vs. Fc/Fc + (THF, [ n Bu 4 N][PF 6 ]; cf. Figure S23), which matches the half‐wave potential E 1/2 =−2.24 V of the diarsene ( Mes TerAs) 2 [26] . DFT studies at the PBE0‐D3/def2‐SVP level of theory show that the energy level of the LUMOs in 1 ( E LUMO =−2.23 eV) and ( Mes TerAs) 2 (−2.19 eV) are similar in the gas phase.…”

Section: Resultssupporting

confidence: 64%

Phosphaarsenes – Combining Phospha‐ and Arsa‐Wittig‐Reagents

Beer,

Siewert,

Schröder

et al. 2024

ChemPlusChem

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Dipnictenes of the type RPn=PnR (Pn = P, As, Sb, Bi) can be viewed as dimers of the corresponding pnictinidenes R−Pn. Phosphanylidene‐ and arsanylidenephosphoranes (R−Pn(PMe3); Pn = P, As) have been shown to be versatile synthetic surrogates for the delivery of pnictinidene fragments. We now report that thermal treatment of 1:1 mixtures of R−P(PMe3) and R’−As(PMe3) gives access to arsaphosphenes of the type RP=AsR’. Three examples are presented and the properties and reactivity of Mes*P=AsDipTer (1) (Mes* = 2,4,6‐tBu3‐C6H2; DipTer = 2,6‐(2,6‐iPr2C6H3)2‐C6H3) were studied in detail. Solid state 31P NMR spectroscopy revealed a large 31P NMR chemical shift anisotropy with a span of ca. 920 ppm for 1 while computational methods were employed to investigate this pronounced magnetic deshielding of the P atom in 1. In the presence of the carbene IMe4 (IMe4 = :C(MeNCMe)2) 1 is shown to be split into the corresponding NHC adducts Mes*P(IMe4) and DipTerAs(IMe4), which is additionally shown for diarsenes.

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“…This motivated the seek for alternative ligand platforms such as NHC (N-heterocyclic carbene), [22] boryl, [23] and gallyl as a tool to tune the reactivity. [24] Specifically, examples of electron transfer, [25,26] cycloaddition [27] and small molecule activation reactions were reported. [28,29] However, despite the progress, it still remains unclear how to easily and systematically improve the reactivity of sterically hindered distibenes and dibismuthenes.…”

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confidence: 99%

Light‐Dependent Reactivity of Heavy Pnictogen Double Bonds

Meleschko,

Palui,

Gomila

et al. 2024

Angew Chem Int Ed

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The chemistry of light dipnictenes has been widely investigated in the last century with remarkable achievements especially for azobenzene derivatives. In contrast, distibenes and dibismuthenes are relatively rare and show very limited reactivity. Herein, we have designed a protocol using visible light to enhance the reactivity of heavy dipnictenes. Exploiting the distinctive π‐π* transition, we have been able to isolate unique examples of dipnictene‐cobalt complexes. The reactivity of the distibene complex was further exploited using red light in the presence of a diazoolefin to access an unusual four‐membered bicyclo[1.1.0]butane analog, containing only a single carbon atom. These findings set the bases to a conceptually new strategy in heavy element double bonds chemistry where visible light is at the front seat of bond activation.

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A diarsene radical anion

Abstract: The isolation of the first diarsene radical anion by reduction of a neutral diarsene is presented. Comprehensive characterisation in conjunction with DFT calculations reveal unpaired spin density residing in the...

Cited by 4 publications

References 37 publications

From Neutral Diarsenes to Diarsene Radical Ions and Diarsene Dications

From Neutral Diarsenes to Diarsene Radical Ions and Diarsene Dications

Phosphaarsenes – Combining Phospha‐ and Arsa‐Wittig‐Reagents

Light‐Dependent Reactivity of Heavy Pnictogen Double Bonds

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