Ein‐, Zwei‐ und Drei‐Elektronen‐Reduktion eines CAAC‐SbCl<sub>3</sub>‐ Addukts

Kretschmer, Robert; Ruiz, David A.; Moore, Curtis E.; Rheingold, Arnold L.; Bertrand, Guy

doi:10.1002/ange.201404849

Cited by 54 publications

(5 citation statements)

References 76 publications

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“…The C−Sb bond length of 6 (2.088(2)−2.094(2) Å) matches well with Bertrand′s base‐stabilized stibinidene(cAAC)SbCl (2.082(5) Å) [23c] featuring a good π‐acceptor cAAC as well as the calculated value for the parent stibabenzene I ‐H (2.05 Å) [34] . Moreover, this value of 6 is also close to the C=Sb bond length calculated for HSb=CH 2 (1.99 Å) [35] as well as of the rare 2,3‐distibabutadienes [R(Me 3 SiO)C=Sb] 2 (R=2,4,6‐Me 3 C 6 H 2 , 2.056(10) Å or 2,4,6‐ t Bu 3 C 6 H 2 , 2.065(5) Å) [3h] .…”

Section: Resultssupporting

confidence: 60%

“…Each of the antimony atoms of 5 is in a formal oxidation state of +1 and has two lone‐pairs of electrons. Thus, like Lewis base‐stabilized neutral ( VII – XII ) [23c,d, 25] and cationic ( XIII ) [26] stibinidene compounds (Figure 2), 5 may be regarded as a rare example of base‐stabilized cyclic bis‐stibinidene species. The weight of major resonance structures (see a–c for IX , Figure 2) depends on the π‐acceptor property of the singlet carbene.…”

Section: Resultsmentioning

confidence: 99%

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Isolation of an Annulated 1,4‐Distibabenzene Diradicaloid

et al. 2023

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The first 1,4‐distibabenzene‐1,4‐diide compound [(ADC)Sb]2 (5) based on an anionic dicarbene (ADC) (ADC=PhC{N(Dipp)C}2, Dipp=2,6‐iPr2C6H3) is reported as a bordeaux‐red solid. Compound 5, featuring a central six‐membered C4Sb2 ring with formally SbI atoms may be regarded as a base‐stabilized cyclic bis‐stibinidene in which each of the Sb atoms bears two lone‐pairs of electrons. 5 undergoes 2 e‐oxidation with Ph3C[B(C6F5)4] to afford [(ADC)Sb]2[B(C6F5)4]2 (6) as a brick‐red solid. Each of the Sb atoms of 6 has an unpaired electron and a lone‐pair. The broken‐symmetry open‐shell singlet diradical solution for (6)2+ is calculated to be 2.13 kcal mol−1 more stable than the closed‐shell singlet. The diradical character of (6)2+ according to SS‐CASSCF (state‐specific complete active space self‐consistent field) and UHF (unrestricted Hartree‐Fock) methods amounts to 36 % and 39 %, respectively. Treatments of 6 with (PhE)2 yield [(ADC)Sb(EPh)]2[B(C6F5)4]2 (7‐E) (E=S or Se). Reaction of 5 with (cod)Mo(CO)4 affords [(ADC)Sb]2Mo(CO)4 (8).

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Section: Resultssupporting

confidence: 60%

Section: Resultsmentioning

confidence: 99%

Isolation of an Annulated 1,4‐Distibabenzene Diradicaloid

et al. 2023

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“…Jedes der Antimonatome von 5 befindet sich in der formalen Oxidationsstufe +1 und besitzt zwei freie Elektronenpaare. Wie die neutralen ( VII – XII ) [23c,d, 25] und kationischen ( XIII ) [26] Lewis‐Basen‐stabilisierten Stibinidenverbindungen (Abbildung 2) kann 5 daher als ein seltenes Beispiel eines cyclischen Bis‐Stibinidens betrachtet werden. Die Gewichtung der wichtigsten Resonanzstrukturen (siehe a‐c für IX , Abbildung 2) hängt von der π‐Akzeptoreigenschaft des Singulettcarbens ab.…”

Section: Ergebnisse Und Diskussionunclassified

“…Die C−Sb‐Bindungslänge von 6 (2.088(2)–2.094(2) Å) stimmt gut mit Bertrand's Base‐stabilisiertem Stibiniden (cAAC)SbCl (2.082(5) Å) (obwohl cAAC ein guter π‐Akzeptor ist), [23c] sowie mit dem berechneten Wert für das Stibabenzol I ‐H (2.05 Å) überein [34] . Außerdem liegt dieser Wert von 6 nahe an der für HSb=CH 2 berechneten C=Sb‐Bindungslänge (1.99 Å), [35] sowie an der des seltenen 2,3‐Distibutadienes [R(Me 3 SiO)C=Sb] 2 (R=2,4,6‐Me 3 C 6 H 2 , 2.056(10) Å oder 2,4,6‐ t Bu 3 C 6 H 2 , 2.065(5) Å) [3h] .…”

Section: Ergebnisse Und Diskussionunclassified

Isolierung eines anellierten 1,4‐Distibabenzol‐Diradikaloids

et al. 2023

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Die erste 1,4-Distabenzol-1,4-diid-Verbindung [(ADC)Sb] 2 (5) auf der Basis eines anionischen Dicarbens (ADC) (ADC = PhC{N(Dipp)C} 2 , Dipp = 2,6-iPr 2 C 6 H 3 ) wird als bordeauxroter Feststoff berichtet. Verbindung 5, die einen zentralen sechsgliedrigen C 4 Sb 2 -Ring mit formalen Sb I -Atomen aufweist, kann als ein Basen-stabilisiertes cyclisches Bis-Stibiniden betrachtet werden, in dem jedes der Sb-Atome zwei freie Elektronenpaare trägt. 5 geht eine 2e-Oxidation mit Ph 3 C[B(C 6 F 5 ) 4 ] ein und bildet [(ADC)Sb] 2 [B(C 6 F 5 ) 4 ] 2 (6) als ziegelroten Feststoff. Jedes der Sb-Atome von 6 hat ein ungepaartes Elektron und ein freies Elektronenpaar. Die offenschalige Singulett-Diradikal-Lösung (broken-symmetry) für ( 6) 2 + ist um 2.13 kcal mol À 1 stabiler als die geschlossenschalige Singulett-Lösung. Der diradikalische Charakter von (6) 2 + beträgt nach SS-CASSCF (state-specific complete active space self-consistent field) und UHF (unrestricted Hartree-Fock) 39 % bzw. 36 %. Die Behandlung von 6 mit (PhE) 2 ergibt [(ADC)Sb(EPh)] 2 [B(C 6 F 5 ) 4 ] 2 (7-E) (E = S oder Se). Die Reaktion von 5 mit (cod)Mo(CO) 4 führt zu [(ADC)Sb] 2 Mo(CO) 4 (8).

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“…synthesized the dicarbene‐substituted diarsenic compound [(CAAC‐3) 2 (μ,η 1:1 ‐As 2 )] ( E ) by reacting CAAC‐3 with AsCl 3 and subsequent reduction [11] . There is also one example that has been reported with the heavier analog antimony which is isostructural to [(CAAC‐n) 2 E 2 ] (E=P ( B ), n=2; As ( E ), n=3) [12] . This product was synthesized by the stepwise reduction of [(CAAC‐2)SbCl 3 ] with potassium graphite.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of Yellow Arsenic towards Cyclic (Alkyl)(Amino) Carbenes (CAACs)

Haimerl

Schwarzmaier

Riesinger

et al. 2023

Chemistry A European J

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Different cyclic (alkyl)(amino)carbenes (CAACs) were reacted with yellow arsenic. Several products [(CAAC‐n)2(μ,η1:1‐As2)] (n=1 (1), 4 (2)), [(CAAC‐2)3(μ3,η1:1:1‐As4)] (3) and [(CAAC‐3)4(μ4,η1:1:1:1‐ As8)] (6) were isolated due to the differing steric properties of CAAC‐1‐4. The products contain As2, As4 or As8 units and represent the first examples of CAACs‐substituted products of yellow arsenic. The reactivity of As4 was compared with the reactivities of P4 and the interpnictogen compound AsP3, which led to a series of phosphorus‐containing derivatives such as ([(CAAC‐3)3(μ3,η1:1:1‐P4)] (4) and [(CAAC‐3)4(μ4,η1:1:1:1‐P8)] (7)) and [(CAAC‐3)3(μ3,η1:1:1‐AsP3)] (5). The products were characterized by spectroscopic and crystallographic methods and DFT computations were performed to clarify their formation pathway.

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Ein‐, Zwei‐ und Drei‐Elektronen‐Reduktion eines CAAC‐SbCl₃‐ Addukts

Cited by 54 publications

References 76 publications

Isolation of an Annulated 1,4‐Distibabenzene Diradicaloid

Isolation of an Annulated 1,4‐Distibabenzene Diradicaloid

Isolierung eines anellierten 1,4‐Distibabenzol‐Diradikaloids

Reactivity of Yellow Arsenic towards Cyclic (Alkyl)(Amino) Carbenes (CAACs)

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Ein‐, Zwei‐ und Drei‐Elektronen‐Reduktion eines CAAC‐SbCl3‐ Addukts

Cited by 54 publications

References 76 publications

Isolation of an Annulated 1,4‐Distibabenzene Diradicaloid

Isolation of an Annulated 1,4‐Distibabenzene Diradicaloid

Isolierung eines anellierten 1,4‐Distibabenzol‐Diradikaloids

Reactivity of Yellow Arsenic towards Cyclic (Alkyl)(Amino) Carbenes (CAACs)

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Ein‐, Zwei‐ und Drei‐Elektronen‐Reduktion eines CAAC‐SbCl₃‐ Addukts