Entering new chemical space with isolable complexes of single, zero-valent silicon and germanium atoms

Yao, Shenglai; Xiong, Yun; Saddington, Artemis; Drieß, Matthias

doi:10.1039/d1cc04100b

Cited by 49 publications

(27 citation statements)

References 107 publications

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“…Zerovalent silicon compounds attract substantial interest because of their unique electronic properties and their synthetic potential as a soluble allotrope of silicon. [1,2] Recently, significant progress has been recorded with the isolation of monoatomic silicon(0) complexes by using the base-stabilization concept. [1,3] However, disilicon(0) complexes remain a rarity, perhaps because of the less effective pπÀ pπ orbital overlap of silicon atoms.…”

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confidence: 99%

Synthesis and Reactivity of N‐Heterocyclic Silylene Stabilized Disilicon(0) Complexes

Jia

Hua

et al. 2022

Angew Chem Int Ed

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Synthesis and reactivity of disilicon(0) complexes are of fundamental and application importance. Herein, we report the development of an N-heterocyclic imino-substituted silylene (1), which has strong σdonating ability and is significantly sterically hindered. The one-pot reaction of this silylene with [IPr!SiCl 2 ] (IPr = 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene) and KC 8 (2 equiv) in THF at À 30 °C leads to a silyleneligated disilicon(0) complex (2), isolated as red crystals in 60 % yield. Characterization data and DFT calculations show that the trans-bent Si 4 skeleton in 2 features a Si 0 =Si 0 double bond with significant π-π bonding and one lone pair of electrons on each of these two Si 0 atoms. Complex 2 reacts readily with phenylacetylene, producing a structurally intriguing silatricyclic complex 6,8-diaza-1,2,5-trisilatricyclo-[3.2.1.0 2,7 ]-oct-3-ene(3), and revealing new aspects of low-valent silicon chemistry.

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confidence: 99%

Synthesis and Reactivity of N‐Heterocyclic Silylene Stabilized Disilicon(0) Complexes

Jia

Hua

et al. 2022

Angew Chem Int Ed

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“…Furthermore, the choice of ortho-carborance based bis(NHSi)s enables the interplay of redox chemistry and also the potentials for small molecule activations through cooperative interactions. [22] The N(I) cationic species exhibit remarkable applications as phase transfer catalysts. The key features of the well-known P(I) cationic systems have been discussed briefly and their potential applications have been discussed, beyond their use as P + transfer reagent.…”

Section: Discussionmentioning

confidence: 99%

“…[21] It has been inferred from the studies that the cyclic ylidones B (Figure 1) having the strongly electron donating supporting ligands such as bis(NHC) or bis(NHSi) (NHC = N-Heterocyclic Carbene; NHSi = N-Heterocyclic Silylene) enhance the electron density on the central atom(0), thereby enabling impressive reactivity, which have been aptly articulated in a recent review. [22] Moving to the Group 15 elements, the pnictogens (Pn=N, P, As, Sb, Bi) in their + 1 oxidation state C, are isoelectronic to the ylidones and thus possess two lone pair of electrons having σand π-symmetry (Figure 1). [23] Among these divalent Pn(I) cations, the chemistry of P(I) cations has flourished significantly, [24] nonetheless the chemistry of the heavier Pn(I) cations are in their infancy.…”

Section: Introductionmentioning

confidence: 99%

Recent Developments in the Chemistry of Pn(I) (Pn=N, P, As, Sb, Bi) Cations

Majumdar

Deb

Balakrishna

2021

Chemistry An Asian Journal

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The Group 15 Pn(I) cations (Pn=N, P, As, Sb and Bi), which are isoelectronic with the donor‐stabilized carbones, have emerged recently. Despite the presence of two lone pair of electrons, the Pn(I) cations are weakly nucleophilic due to their inherent positive charge. Strongly electron‐donating supporting ligands including zwitterionic forms have been used to enhance their Lewis basicity. Furthermore, the chelating effect of cyclic ligand systems proved effective in increasing their nucleophilicity. The strategies involved in successfully isolating the fleeting Sb(I) and Bi(I) cations as the recent most achievements in this field have been discussed. The syntheses, structure, bonding situations and reactivity of the Pn(I) cations are discussed. An outlook on the periodic trends and future applications of these electronically unique electron‐rich cationic moieties have been provided.

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“…:E=L) and bent allene (L=E=L) depending on the nature of ligands. [2,13] Heavier carbene analogues such as silylenes and germylenes appear to be a prominent ligand class in this field as a result of their superior σ-donating and partial π-accepting ability. [2][3][4][5][6][7][8][9][10][11] In their seminal work, Kira and Iwamoto reported the isolation of a series of heavier allene congeners (A and B in Scheme 1).…”

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An Isolable Bis(Germylene)‐Stabilized Plumbylone

et al. 2022

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We report herein the synthesis of a stable plumbylone (3) by reduction of a bromodigermylplumbylene (2) with 2.2 equiv of potassium graphite (KC 8 ). The molecular structure of 3 was established by a singlecrystal X-ray diffraction study and features a twocoordinated Pb center with an acute GeÀ PbÀ Ge bond angle. Computational studies showed that this complex (3) possesses a singlet electronic ground state with a Pb 0 center. Its high thermal stability can be most likely ascribed to the delocalization of π electrons over the GeÀ PbÀ Ge moiety. A preliminary reactivity study demonstrates that complex 3 can deliver Pb 0 atoms to an organic azide producing a tetrameric imido complex [(PbNDipp) 4 ] (Dipp = 2,6-i Pr-C 6 H 3 , 4) and perform a metathesis reaction with GeCl 2 •dioxane to produce a bis(germylene)-stabilized germylone (5), highlighting the synthetic utility of 3.

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Entering new chemical space with isolable complexes of single, zero-valent silicon and germanium atoms

Abstract: Monatomic zero-valent silicon and germanium complexes (named silylones and germylones) stabilised by neutral donating ligands emerged only recently as a new class of low-valent Group 14 element compounds. Featuring four...

Cited by 49 publications

References 107 publications

Synthesis and Reactivity of N‐Heterocyclic Silylene Stabilized Disilicon(0) Complexes

Synthesis and Reactivity of N‐Heterocyclic Silylene Stabilized Disilicon(0) Complexes

Recent Developments in the Chemistry of Pn(I) (Pn=N, P, As, Sb, Bi) Cations

An Isolable Bis(Germylene)‐Stabilized Plumbylone

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