Mehrkernige Eisen/Tantal- und Tantal-Komplexe mit As<sub>n</sub>-Liganden

The generation and handling of the light-sensitive and metastable yellow arsenic (As4) is extremely challenging. In view of recent breakthroughs in synthesizing As4 storage materials and transfer reagents, the more intensive use of yellow arsenic as a source for further reactions can be expected. Given these aspects, the current stage of knowledge of the direct use of As4 is comprehensively summarized in the present review, which lists the activation of As4 by main group elements as well as transition metal compounds (including the f-block elements). Moreover, it also partly compares the reaction outcomes in relation to the corresponding reactions of P4. The possibility of using alternative sources for generating arsenic moieties and compounds is also discussed. The release of As4 molecules from precursor compounds and the use of transfer reagents for polyarsenic entities open up new synthetic pathways to avoid the direct generation of yellow arsenic solutions and to ensure its smooth usage for subsequent reactions.

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“…Molecular structures of 6.1-5 (left) and 6.1-7 (right). Figure created by authors from data in refs and .…”

Section: Reactivity Of As4 Toward Transition Metal Complexesmentioning

confidence: 99%

“…The distance between the two As atoms at respective ends of the chain is 3.745 Å, outside of the accepted range of As···As interactions. Complex 6.1-7 can also be obtained by the reaction of [Cp*Fe(η 5 -As 5 )] with [Cp″Ta(CO) 4 ] in decalin at 190 °C …”

Section: Reactivity Of As4 Toward Transition Metal Complexesmentioning

confidence: 99%

The Chemistry of Yellow Arsenic

2019

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“…1). 15 Moreover, the fragmentation into partially separated P 2 and P 3 units within the coordination sphere of group 8 metals such as Fe and Ru was realised by Scherer et al (V, {ML n } = {Cp″Ru} or {Cp″Fe}; Fig. 1).…”

Section: Introductionmentioning

confidence: 95%

Homo- and heterobimetallic transition metal cluster derived from [Cp*Fe(η⁵-E₅)] (E = P, As) – unprecedented structural motifs of the resulting polypnictogen ligands

Dinauer,

Szlosek,

Piesch

et al. 2024

Dalton Trans.

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“…Similar reactions involving heavier and precious metals of group 9 (Rh, Ir) proceed more selectively under milder conditions, but the isolated compounds still contain CO ligands ( A – C , Scheme ). , In contrast, the thermolysis of 1a , b with [Cp″Ta(CO) 4 ] (Cp″ = 1,3-ditertbutyl-cyclopentadienyl) proceeds quite selectively, and [(Cp*Fe)(Cp″Ta)(μ,η 4 :η 3 -E 5 )] (E = P ( D ) and As ( E ), Scheme ) is formed as the only isolatable product. , All the mentioned thermolysis reactions yield thermodynamically stable products. Moreover, in the case of polyarsenic (As n ) complexes, their formation cannot be monitored by NMR spectroscopy, and no further transformations of these products have yet been reported.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of a Heterobimetallic Arsenic Triple-Decker Complex and Its Fragmentation Chemistry

Piesch

Scheer

2020

Organometallics

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The synthesis of the metastable triple-decker complex [(Cp*Fe)(Cp‴Co)(μ,η 5 :η 4 -As 5 )] (3) (Cp* = pentamethyl-cyclopentadienyl, Cp‴ = 1,2,4-tritertbutyl-cyclopentadienyl) is reported. 3 is sensitive toward thermal activation (and in solutions of acetonitrile), which converts 3 selectively into [(Cp*Fe)(Cp‴Co)(μ,η 3 :η 3 -As 3 )] ( 4) and [(Cp*Fe) 2 (Cp‴Co) 2 (μ 4 ,η 4 :η 4 :η 4 :η 3 -As 11 )] (5). Harsher thermal reaction conditions lead to a further fragmentation into [Cp*Fe(η 5 -As 5 )] (1b), [(Cp‴Co) 2 (μ,η 2 :η 2 -As 2 ) 2 ] (6), and [(Cp*Fe) 2 (Cp‴Co)(μ 3 ,η 2 :η 2 :η 2 -As 3 ) 2 ] ( 7), which can be completed by longer reaction times or higher temperatures. The fragmentation was investigated by variable-temperature and time-dependent NMR spectroscopy, and a fine-tuning of the selectivity can be achieved by applying different reaction conditions. All compounds were fully characterized, and their electronic structures were elucidated by DFT calculations.

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Mehrkernige Eisen/Tantal- und Tantal-Komplexe mit As_n-Liganden

Cited by 11 publications

References 8 publications

The Chemistry of Yellow Arsenic

The Chemistry of Yellow Arsenic

Homo- and heterobimetallic transition metal cluster derived from [Cp*Fe(η⁵-E₅)] (E = P, As) – unprecedented structural motifs of the resulting polypnictogen ligands

Synthesis of a Heterobimetallic Arsenic Triple-Decker Complex and Its Fragmentation Chemistry

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Mehrkernige Eisen/Tantal- und Tantal-Komplexe mit Asn-Liganden

Cited by 11 publications

References 8 publications

The Chemistry of Yellow Arsenic

The Chemistry of Yellow Arsenic

Homo- and heterobimetallic transition metal cluster derived from [Cp*Fe(η5-E5)] (E = P, As) – unprecedented structural motifs of the resulting polypnictogen ligands

Synthesis of a Heterobimetallic Arsenic Triple-Decker Complex and Its Fragmentation Chemistry

Contact Info

Product

Resources

About

Mehrkernige Eisen/Tantal- und Tantal-Komplexe mit As_n-Liganden

Homo- and heterobimetallic transition metal cluster derived from [Cp*Fe(η⁵-E₅)] (E = P, As) – unprecedented structural motifs of the resulting polypnictogen ligands