Pentafluoroethyl Bismuth Compounds

Solyntjes, Sven; Bader, Julia; Neumann, Beate; Stammler, Hans‐Georg; Ignat’ev, Nikolai; Hoge, Berthold

doi:10.1002/chem.201604910

Cited by 38 publications

(40 citation statements)

References 48 publications

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“…Consistently, the compound Sn(C 2 F 5 ) 4 as well as the anion [Sn(C 2 F 5 ) 5 ] − represent valuable precursors for the generation of LiC 2 F 5 upon the addition of n‐ butyllithium . A comparable reactivity is also observed for pentafluoroethylphosphorus compounds . This procedure for the generation of LiC 2 F 5 has an advantage with respect to the established procedure of deprotonating gaseous HC 2 F 5 as it does not require the tedious handling of gases.…”

Section: Homoleptic Pentafluoroethyl‐element Compoundsmentioning

confidence: 74%

“…[20] Ac omparable reactivity is also observed for pentafluoroethylphosphorus compounds. [46] This procedure for the generation of LiC 2 F 5 has an advantage with respect to the established procedure of deprotonating gaseous HC 2 F 5 as it does not require the tedious handling of gases.I no rder to establish the pentakis(pentafluoroethyl)stannate anion as an alternative precursor for the highly reactive which warrants ag as-free generation of LiC 2 F 5 . [47] Pentafluoroethylationr eactions using [PPh 4 ][Sn(C 2 F 5 ) 5 ]w ere effected by the addition of n-butyllithium to ad iethyl ether solution of the stannate salt at À60 8Ca nd the subsequenta ddition of suitable electrophiles (Ph 2 CO, PhCHO, P(NEt 2 ) 2 Cl) (Scheme 11).…”

Section: Homoleptic Pentafluoroethyl-element Compoundsmentioning

confidence: 99%

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Pentafluoroethylated Compounds of Silicon, Germanium and Tin

Wiesemann

Hoge

2018

Chemistry A European J

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In this contribution we present an account on pentafluoroethylated compounds of silicon, germanium and tin. The pronounced electron-withdrawing effect of the pentafluoroethyl group leads to a markedly increased Lewis acidity at the central atom which results in the stabilization of hypervalent complexes, anionic element(II) species as well as remarkable reactivities of element-element and element-hydrogen bonds. By addition to unsaturated C-C bonds or by reaction with organic halides as well as transition-metal complexes the molecules bearing a pentafluoroethyl-element group are readily accessible. Moreover, the utilization of pentafluoroethyl groups facilitates the formation of donor-stabilized germylenes and stannylenes. A series of such compounds serves as suitable pentafluoroethylation reagents. Conversely to the well-studied trifluoromethyl derivatives these compounds frequently exhibit a higher thermostability, which allows a more convenient handling.

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Section: Homoleptic Pentafluoroethyl‐element Compoundsmentioning

confidence: 74%

Section: Homoleptic Pentafluoroethyl-element Compoundsmentioning

confidence: 99%

Pentafluoroethylated Compounds of Silicon, Germanium and Tin

Wiesemann

Hoge

2018

Chemistry A European J

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“…Preliminary mechanistic investigations point out at a catalytic platform involving extremely reactive Bi(III) hydride intermediates (Figure 1C). 18 To the best of our knowledge, this is the first example of a catalytic redox cycle in the pnictogens group maneuvering in a Pn(I)/Pn(III) redox cycle.…”

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confidence: 88%

Bi(I)-Catalyzed Transfer-Hydrogenation with Ammonia-Borane

2019

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A catalytic transfer-hydrogenation utilizing a well-defined Bi(I) complex as catalyst and ammonia-borane as transfer agent has been developed. This transformation represents a unique example of low-valent pnictogen catalysis cycling between oxidation states I and III, and proved useful for the hydrogenation of azoarenes and the partial reduction of nitroarenes. Interestingly, the bismuthinidene catalyst performs well in the presence of low-valent transition-metal sensitive functional groups and presents orthogonal reactivity compared to analogous phosphorus-based catalysis. Mechanistic investigations suggest the intermediacy of an elusive bismuthine species, which is proposed to be responsible for the hydrogenation and the formation of hydrogen.

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“…Another reaction pathway towards dibismuthanes is the reaction with hydride sources. Here, a secondary bismuthane is produced in the first reaction step, decomposing to the corresponding dibismuthane under elimination of dihydrogen [18–22] . Such dibismuthanes are known to react with element‐element bonds and have successfully been used for the activation of chalcogens [16,23–26] and even white phosphorus [19] .…”

Section: Introductionmentioning

confidence: 99%

2,6‐Diisopropylphenyl‐Substituted Bismuth Compounds: Synthesis, Structure, and Reactivity

et al. 2021

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The 2,6‐diisopropylphenyl (Dipp) substituent is introduced to diaryl bismuth chemistry. Dipp2BiBr (1‐Br) was prepared by a Grignard reaction and subsequently used as precursor for synthesis of the other diaryl halido bismuthanes Dipp2BiX (1‐X, X=F, Cl, I) and the corresponding triflate Dipp2BiOTf (1‐OTf). Moreover, 1,1,2,2‐tetrakis(2,6‐diisopropylphenyl)dibismuthane (2) was prepared. All isolated compounds were characterized via single crystal X‐ray diffraction analysis, NMR spectroscopy, IR spectroscopy, and elemental analysis. Furthermore, the reactivity of a dibismuthane towards elemental sulfur was investigated, and the formed dibismuthanyl tri‐ and pentasulfide (3 a, 3 b) were characterized by single crystal X‐ray analysis. Functionalization of the diaryl halido bismuthanes with LiPtBu2 or tBu2PTMS (TMS=SiMe3) gives access to the interpnictogen compound Dipp2Bi−PtBu2 (4), which shows a rare example of a covalent Bi−P bond.

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Pentafluoroethyl Bismuth Compounds

Cited by 38 publications

References 48 publications

Pentafluoroethylated Compounds of Silicon, Germanium and Tin

Pentafluoroethylated Compounds of Silicon, Germanium and Tin

Bi(I)-Catalyzed Transfer-Hydrogenation with Ammonia-Borane

2,6‐Diisopropylphenyl‐Substituted Bismuth Compounds: Synthesis, Structure, and Reactivity

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