Eine Verbindung mit einer Si‐C‐Dreifachbindung

The first divinyldiarsenes[ {(NHC)C(Ph)}As] 2 (NHC = IPr 3a,S IPr 3b;I Pr = C{(NAr)CH} 2 ;S IPr = C{(NAr)CH 2 } 2 ;A r = 2,6-iPr 2 C 6 H 3 )a re reported. Compounds 3a and 3b were prepared by the reduction of corresponding chlorides {(NHC)C(Ph)}AsCl 2 (NHC = IPr 2a,S IPr 2b)w ith Mg. Calculationsr evealed as mall HOMO-LUMO energy gap of 3.86 (3a)a nd 4.24 eV (3b). Treatment of 3a with (Me 2 S)AuCl led to the cleavage of the As=As bond to restore 2a,w hich is expected to proceed via the diarsane [{(IPr)C(Ph)}AsCl] 2 (4). Remarkably, 4 as wella s2a can be selectively accessed on treatment of 3a with an appropriate amount of C 2 Cl 6 .M oreover, 3a readily reacts with PhEEPh( E= Se or Te)a tr oom temperature to give {(IPr)C(-Ph)}As(EPh) 2 (E = Se 5a;T e5b), revealing the cleavageo f As=As and EÀEb onds and the formation of AsÀEb onds. Such highly selectivestepwise oxidation (3a!4!2a)a nd bond metathesis (3a!5a,b)r eactionsa re unprecedented in main-group chemistry.

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Crystalline Divinyldiarsenes and Cleavage of the As=As Bond

Sharma

Blomeyer

Neumann

et al. 2019

Chemistry A European J

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Distannabarrelenes with Three Coordinated Sn^II Atoms

Sharma

Glodde

Neumann

et al. 2020

Chemistry A European J

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Crystalline 1,4‐distannabarrelene compounds [(ADCAr)3Sn2]SnCl3 (3‐Ar) (ADCAr={ArC(NDipp)2CC}; Dipp=2,6‐iPr2C6H3, Ar=Ph or DMP; DMP=4‐Me2NC6H4) derived from anionic dicarbenes Li(ADCAr) (2‐Ar) (Ar=Ph or DMP) have been reported. The cationic moiety of 3‐Ar features a barrelene framework with three coordinated SnII atoms at the 1,4‐positions, whereas the anionic unit SnCl3 is formally derived from SnCl2 and chloride ion. The all carbon substituted bis‐stannylenes 3‐Ar have been characterized by NMR spectroscopy and X‐ray diffraction. DFT calculations reveal that the HOMO of 3‐Ph (ϵ=−6.40 eV) is mainly the lone‐pair orbital at the SnII atoms of the barrelene unit. 3‐Ar readily react with sulfur and selenium to afford the mixed‐valence SnII/SnIV compounds [(ADCAr)3SnSn(E)](SnCl6)0.5 (E=S 4‐Ar, Ar=Ph or DMP; E=Se 5‐Ph).

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Eine Verbindung mit einer Si‐C‐Dreifachbindung

Abstract: Eine alte Reaktion, aber ein erstaunliches Produkt: Fast 100 Jahre nach Curtius' Synthese von Alkinen aus Bisdiazoverbindungen fand das gleiche Reaktionsprinzip Verwendung für die Synthese eines Silins, einer Verbindung mit einer Si‐C‐Dreifachbindung.

Cited by 2 publications

References 29 publications

Crystalline Divinyldiarsenes and Cleavage of the As=As Bond

Crystalline Divinyldiarsenes and Cleavage of the As=As Bond

Distannabarrelenes with Three Coordinated Sn^II Atoms

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Eine Verbindung mit einer Si‐C‐Dreifachbindung

Abstract: Eine alte Reaktion, aber ein erstaunliches Produkt: Fast 100 Jahre nach Curtius' Synthese von Alkinen aus Bisdiazoverbindungen fand das gleiche Reaktionsprinzip Verwendung für die Synthese eines Silins, einer Verbindung mit einer Si‐C‐Dreifachbindung.

Cited by 2 publications

References 29 publications

Crystalline Divinyldiarsenes and Cleavage of the As=As Bond

Crystalline Divinyldiarsenes and Cleavage of the As=As Bond

Distannabarrelenes with Three Coordinated SnII Atoms

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Product

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Distannabarrelenes with Three Coordinated Sn^II Atoms