Different Reactivity of As<sub>4</sub>towards Disilenes and Silylenes

Seitz, Andreas E.; Eckhardt, Maria; Sen, Sakya S.; Erlebach, Andreas; Peresypkina, Eugenia V.; Roesky, Herbert W.; Sierka, Marek; Scheer, Manfred

doi:10.1002/anie.201701740

Cited by 26 publications

(13 citation statements)

References 55 publications

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“…101 By contrast, the reaction of 149 with As 4 in toluene leads to the formation of the unprecedented As 10 cage compound 151 featuring a nortricyclane core. 102 The Si-As bond of the exocyclic substituents in 151 can be regarded as an elongated double bond or an ion compound with the negative charge localised at the As atom and the positive charge over both N atoms in the heterocycle.…”

Section: Degradation Of P 4 and Asmentioning

confidence: 99%

Where silylene–silicon centres matter in the activation of small molecules

2020

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Section: Degradation Of P 4 and Asmentioning

confidence: 99%

Where silylene–silicon centres matter in the activation of small molecules

2020

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“…The solid state structure of 12 (Figure ) contains a bridging Si–H···Li contact, leading to tetrahedral geometry at Li1 and a rather acute Si–As–Li angle of 68.63(1)°. The high charge density at As1, due to its metalation, leads to a highly contracted Si–As bond length in 12 (δ = 2.2402(8) Å), which is essentially as short as the majority of “free” SiAs bonds, including the 1,2-dihydrosilaarsene D reported by us previously (d(Si–As) = 2.214 Å). , Indeed, the Si–As bond in 12 is considerably shorter than that in closely related 11 , testament to the charge separation in the As–Li bond relative to the As–Ni bond. Despite this, the Ni–As bond in 12 is longer than that in 11 , at 2.4015 Å, with a similar lengthening observed for the Ni–Si bond (d(Si1–Ni1) = 2.233(1) Å).…”

Section: Resultsmentioning

confidence: 76%

Versatile Tautomerization of EH₂-Substituted Silylenes (E = N, P, As) in the Coordination Sphere of Nickel

2019

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The synthesis and tautomerization of a "halfparent" aminosilylene and its heavy P-and As-analogues ( TMS LSi-EH 2 ; E = N, P, As; TMS L = N(SiMe 3 )(2,6-i Pr 2 C 6 H 3 )) in the coordination sphere of nickel(0) to give the corresponding side-on η 2 -RSi(H)EH and RH 2 Si-E ("silylpnictinidene") nickel complexes are reported. These complexes can be accessed through salt metathesis reactions of the lithium dihydropnictides LiEH 2 with the acyclic chlorosilylene nickel(0) complex 1, [ TMS L(Cl)Si → Ni(NHC) 2 ; NHC = :C[( i Pr)NC(Me)] 2 ). In addition, we report the facile E−H bond activation reactions of EH 3 with 1, which furnished a silyl nickel(II) complex through NH 3 activation, but phosphido and arsenido complexes in the activation of PH 3 and AsH 3 , respectively. Notably, reaction of 1 with LiNH 2 leads to the acyclic bis(amido)silylene complex [ TMS L(H 2 N)Si → Ni(NHC) 2 ] 5, which does not undergo N−H proton migration to silicon(II) under ambient conditions. The transformation of the P-and As-analogues of 1 furnishes directly the respective side-on SiE Ni complexes (nickelacycles), [η 2 -{ TMS L(H)Si E(H)}Ni(NHC) 2 ] (E = P, 6; E = As, 9). These nickelacycles show a vastly different stability in solutions. While 6 is stable for several days at ambient temperature, 9 undergoes further rearrangement processes within minutes of its formation. Given the high acidity of the As−H proton in 9, however, this moiety can be trapped as a highly charge separated metalated-η 2 -silaarsene nickel complex 12 that is best described as an [AsSiNi] nickelacycle with Si−As multiple bond character. Taken as a whole, these results give, for the first time, insights into the relative stability of the tautomeric forms of side-on silaldimine transition metal complexes. The electronic nature and the rearrangement processes of these compounds were also investigated by quantum chemical calculations.

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“…1 was later reproduced by Roesky and co-workers in 68% yield by utilizing (Me 5 C 5 )SiHCl 2 precursor with KN(TMS) 2 in a single-step procedure . This modified procedure of 1 boosted further exploration of its reactivity and led to the isolation of Si 2 O 2 and Si 2 S 2 ring compounds along with P 4 and As 4 activation. − Nonetheless, the reactivity of 1 is only limited to this handful of examples (Chart ), but they are different than the usual disilenes.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of (TMS)₂N(η¹-Cp)Si═Si(η¹-Cp)N(TMS)₂ toward the Halides of Groups 13–15

et al. 2021

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In this paper, we have demonstrated the unique reactivity of a previously reported disilene [(TMS)2N(η1-Me5C5)SiSi(η1-Me5C5)N(TMS)2] (1) with the halides of groups 13–15, which resulted in the formation of silicon–E (E = B, Al, Ge, P) bonds. Treatment of 1 with Lewis acidic BCl3 led to the formation of a cationic boron species [Cp*BSi(Cl)2N(TMS)2)][BCl3SiCl3] (2). In contrast, the reaction of 1 with BCy2Cl afforded an oxidative addition product [(TMS)2N(η1-Me5C5)Si(BCy2)(Cl)] (3) via the insertion of a Si(II) atom into the B–Cl bond. Extending the reaction with its higher congener led to classical Lewis acid-base adducts, (TMS)2N(η1-Me5C5)Si→AlCl3 (4) and (TMS)2N(η1-Me5C5)Si→AlBr3 (5), respectively. The reaction of GeCl2 with 1 proceeded in a completely different manner and resulted in a hybrid dendrimeric compound [HGe(Si(Cl)2N(TMS)2)3] (6), whereas, with SnCl2, it led to Cp*SnCl (7). Lastly, the reaction of Ph2PCl followed the same pattern like Cy2BCl and led to the formation of an oxidative addition product [(TMS)2N(η1-Me5C5)Si(PPh2)(Cl)] (9) with a Si–P bond.

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Different Reactivity of As₄towards Disilenes and Silylenes

Cited by 26 publications

References 55 publications

Where silylene–silicon centres matter in the activation of small molecules

Where silylene–silicon centres matter in the activation of small molecules

Versatile Tautomerization of EH₂-Substituted Silylenes (E = N, P, As) in the Coordination Sphere of Nickel

Reactivity of (TMS)₂N(η¹-Cp)Si═Si(η¹-Cp)N(TMS)₂ toward the Halides of Groups 13–15

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Different Reactivity of As4towards Disilenes and Silylenes

Cited by 26 publications

References 55 publications

Where silylene–silicon centres matter in the activation of small molecules

Where silylene–silicon centres matter in the activation of small molecules

Versatile Tautomerization of EH2-Substituted Silylenes (E = N, P, As) in the Coordination Sphere of Nickel

Reactivity of (TMS)2N(η1-Cp*)Si═Si(η1-Cp*)N(TMS)2 toward the Halides of Groups 13–15

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Different Reactivity of As₄towards Disilenes and Silylenes

Versatile Tautomerization of EH₂-Substituted Silylenes (E = N, P, As) in the Coordination Sphere of Nickel

Reactivity of (TMS)₂N(η¹-Cp)Si═Si(η¹-Cp)N(TMS)₂ toward the Halides of Groups 13–15