Stabilization of Reactive Nitrene by Silylenes without Using a Reducing Metal

Ding, Yi; Sarkar, Samir Kumar; Nazish, Mohd; Muhammed, Shahila; Lüert, Daniel; Ruth, Paul Niklas; Legendre, Christina M.; Herbst‐Irmer, Regine; Parameswaran, Pattiyil; Yang, Zhi; Roesky, Herbert W.

doi:10.1002/anie.202110456

Cited by 18 publications

(26 citation statements)

References 53 publications

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“…The unligated Si(I)-based disilylene species I shows stoichiometry-dependent reactivity toward trimethylsilyl azide, forming either a silaazatriene or a silaimine product. , Roesky and co-workers described ring opening of their disilaborirane species VI with TMSN 3 , forming a 1-aza-2,3-disila-4-boretidine derivative (Scheme ). We observed selective conversion of 3 with 1 equiv of TMSN 3 to give the unique azide adduct 4 after 1 h at 40 °C in benzene solution.…”

Section: Resultsmentioning

confidence: 99%

Reactivity of a Unique Si(I)–Si(I)-Based η²-Bis(silylene) Iron Complex

Liu

Zwart

et al. 2022

Inorg. Chem.

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In this paper, we report the synthesis of a unique silicon(I)-based metalla-disilirane and report on its reactivity toward TMS-azide and benzophenone. Metal complexes containing disilylenes ((bis)silylenes with a Si–Si bond) are known, but direct ligation of the Si(I) centers to transition metals always generated dinuclear species. To overcome this problem, we targeted the formation of a mononuclear iron(0)–silicon(I)-based disilylene complex via templated synthesis, starting with ligation of two Si(II) centers to iron(II), followed by a two-step reduction. The DFT structure of the resulting η 2 -disilylene-iron complex reveals metal-to-silicon π-back donation and a delocalized three-center–two-electron (3c–2e) aromatic system. The Si(I)–Si(I) bond displays unusual but well-defined reactivity. With TMS-azide, both the initial azide adduct and the follow-up four-membered nitrene complex could be isolated. Reaction with benzophenone led to selective 1,4-addition into the Si–Si bond. This work reveals that selective reactions of Si(I)–Si(I) bonds are made possible by metal ligation.

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Section: Resultsmentioning

confidence: 99%

Reactivity of a Unique Si(I)–Si(I)-Based η²-Bis(silylene) Iron Complex

Liu

Zwart

et al. 2022

Inorg. Chem.

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“…Without doubt, the most studied 1,2‐disilylene is the three‐coordinate, amidinate‐ligated compound, [{PhC(NBu t ) 2 }Si] 2 , which was reported by Roesky and co‐workers in 2009 [3] . Since that time, this compound has been utilized in a remarkable array of reactions, most notably for the reductive activation of numerous unsaturated small molecule substrates [2, 4] . As far as we are aware, the only other structurally characterized amidinate‐stabilized 1,2‐disilylene, is the bulkier, deep blue system, [{ArC(NDip) 2 }Si] 2 1 (Dip=2,6‐diisopropylphenyl, Ar=4‐C 6 H 4 Bu t ), reported by our group in 2011 [5] .…”

Section: Methodsmentioning

confidence: 99%

“…[3] Since that time, this compound has been utilized in a remarkable array of reactions, most notably for the reductive activation of numerous unsaturated small molecule substrates. [2,4] As far as we are aware, the only other structurally characterized amidinate-stabilized 1,2-disilylene, is the bulkier, deep blue system, [{ArC(NDip) 2 }Si] 2 1 (Dip = 2,6-diisopropylphenyl, Ar = 4-C 6 H 4 Bu t ), reported by our group in 2011. [5] In contrast to [{PhC(NBu t ) 2 }Si] 2 , the reactivity of 1 has been poorly studied.…”

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confidence: 94%

Activation of CO Using a 1,2‐Disilylene: Facile Synthesis of an Abnormal N‐Heterocyclic Silylene

et al. 2022

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Reaction of the 1,2‐disilylene, [{ArC(NDip)2}Si]2 1 (Dip=2,6‐diisopropylphenyl, Ar=4‐C6H4But), with CO proceeds via insertion of CO into one Si−N bond, and Si−Si bond cleavage, to cleanly give the bis(silylene), {ArC(NDip)2}Si(:)OnormalCnormalSnormali(:)(normalNnormalDnormalinormalp)2normalC‾ Ar 2, under ambient conditions. The reaction can be partially reversed when solutions of 2 are subjected to UV irradiation. The five‐membered heterocyclic fragment of 2 represents the first silicon analogue of an “abnormal” N‐heterocyclic carbene (aNHC), a view which is substantiated by a computational analysis of the compound. Reaction of 2 with [Mo(CO)6] under UV light affords the chelate complex, [Mo(CO)4(κ2‐Si,Si‐2)] 3, while reaction with [Fe(CO)5] gives the unusual silyleneyl bridged complex, [{Fe2(CO)6}{μ‐Si[(NDip)2CAr]}2] 4. The same coordination complexes can be accessed by reaction of 1 with [Mo(CO)6] or [Fe(CO)5] under UV light. As is the case for aNHCs, d‐block metal complexes of bis(silylene) 2 could prove useful as bespoke catalysts for organic transformations.

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“…9 Very recently, our group studied the reaction of organic azide with bis-silylene in the different molar ratios, which resulted in the formation of different compounds (D and E) in Chart 1. 10 The reactivity of Me 3 SiN 3 azide with moieties of low-valent silicon provoked the question of whether a similar organic azide reactivity would be experimental with heavier germylene analogues. 4a As we know, the low-valent Si species are susceptible to converting into Si IV via oxidation.…”

Section: ■ Introductionmentioning

confidence: 99%

Insertion Reaction of Me₃SiN₃with Bis(germylene)

et al. 2022

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Herein, we describe the redox reaction of bis(germylene) PhC(N t Bu)2Ge–Ge(N t Bu)2CPh with different equivalents of Me3SiN3 affording two distinct products. The reaction of Me3SiN3 with bis-germylene in a 1:1 molar ratio results in compound 1 at −78 °C; however, treatment of bis-germylene with a 2.1 equiv of Me3SiN3 at room temperature results in compound 2. The formation of 1 and 2 can be rationalized by two successive 3 + 1 cycloadditions of Me3SiN3 with the germanium center of bis(germylene) and N2 elimination. All of the compounds are well-characterized by various spectroscopic techniques and single-crystal X-ray structural analyses. Density functional theory (DFT) calculations suggest that compound 2 has a dicoordinated nitrogen atom, which is stabilized by hyperconjugative interactions, resulting in pseudo-germylimine moiety. However, the dicoordinated nitrogen atom shows high basicity as indicated by proton affinity values. These are rare examples of isolated products that show insertion as well as simultaneous redox properties of bis(germylene).

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Stabilization of Reactive Nitrene by Silylenes without Using a Reducing Metal

Cited by 18 publications

References 53 publications

Reactivity of a Unique Si(I)–Si(I)-Based η²-Bis(silylene) Iron Complex

Reactivity of a Unique Si(I)–Si(I)-Based η²-Bis(silylene) Iron Complex

Activation of CO Using a 1,2‐Disilylene: Facile Synthesis of an Abnormal N‐Heterocyclic Silylene

Insertion Reaction of Me₃SiN₃with Bis(germylene)

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Stabilization of Reactive Nitrene by Silylenes without Using a Reducing Metal

Cited by 18 publications

References 53 publications

Reactivity of a Unique Si(I)–Si(I)-Based η2-Bis(silylene) Iron Complex

Reactivity of a Unique Si(I)–Si(I)-Based η2-Bis(silylene) Iron Complex

Activation of CO Using a 1,2‐Disilylene: Facile Synthesis of an Abnormal N‐Heterocyclic Silylene

Insertion Reaction of Me3SiN3with Bis(germylene)

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Reactivity of a Unique Si(I)–Si(I)-Based η²-Bis(silylene) Iron Complex

Reactivity of a Unique Si(I)–Si(I)-Based η²-Bis(silylene) Iron Complex

Insertion Reaction of Me₃SiN₃with Bis(germylene)