A soluble molecular variant of the semiconducting silicondiselenide

Mondal, Kartik Chandra; Roy, Sudipta; Dittrich, Birger; Maity, Bholanath; Dutta, Sayan; Koley, Debasis; Vasa, Suresh K.; Linser, Rasmus; Dechert, Sebastian; Roesky, Herbert W.

doi:10.1039/c5sc01516b

Cited by 36 publications

(20 citation statements)

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“…As imilar Si À Se distance was reported by Roesky in the terminal Si IV = Se moiety of (cAAC) 2 Si 2 Se 4 (2.151 (1) ). [9] Thus compound 2 could be formally regarded as amonomolecular SiSe species supported by bis-NHC and GaCl 3 .T he crystal structure of compound 3 (Figure 2, left) is isostructural with its sulfur analogue (bis-NHC)Si(=S)SGaCl 3 described by us very recently. [8] Tw od ifferent types of Si À Se bonds are observed in the structure.T he long Si1 À Se2 of 2.241(6) is close to the single-bond values reported for the silicon diselenide polymer (SiSe 2 ) n (2.275 ), [13] while the short Si1ÀSe1 bond of 2.129(2) resembles the Si=Se bond found in 2 (2.135(1) ).…”

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confidence: 84%

“…Interestingly,t he 29 Si{ 1 H} NMR spectrum of 4 displays an upfield-shifted resonance at d = À143.9 ppm, while the 125 Te{ 1 H} NMR spectrum shows as ignal at d = À1120 ppm comparable to the b-diketiminato ligand-supported Si IV = Te species (d = À1076.7 and À1105.5 ppm). [9] Compound 4 crystallizes in the monoclinic space group P2 1 /c (Figure 2r ight). Thes ingle-crystal X-ray diffraction study reveals ad istorted tetrahedral structure for the silicon center which is coordinated by the bis-NHC ligand and features two terminal tellurium atoms.T he two Si À Te distances are slightly different (Si1ÀTe 12 .389(4) and Si1À Te 22 .436(2) ).…”

Section: Communicationsmentioning

confidence: 99%

“…[7,8] Recently,R oesky et al described ad imeric SiSe 2 complex supported by ac yclic alkyl-(amino)carbene (cAAC). [9] Furthermore,B aceiredo and Kato et al reported am onomeric SiO 2 complex using donor-acceptor interactions. [10] Herein, we report the remarkably facile access to the first isolable monomeric SiSe complexes as well as the first example of the structurally characterized monomolecular SiTe 2 species supported only by Lewis donors.…”

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confidence: 99%

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Taming Silicon Congeners of CO and CO₂: Synthesis of Monomeric Si^II and Si^IV Chalcogenide Complexes

et al. 2017

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The synthesis of the unprecedented monomeric Si II selenide complex (bis-NHC)Si=Se!GaCl 3 2 (bis-NHC = bis-Nh eterocyclic carbene,H 2 C[{NC(H)=C(H)N(Dipp)}CD] 2 , Dipp = 2,6-iPr 2 C 6 H 3 ), bearing the elusive SiSe ligand as ah eavy CO homologue by the reaction of the silylone-GaCl 3 adduct (bis-NHC)Si!GaCl 3 1 with elemental selenium in acetonitrile,isreported. The similar conversion of 1 with excess selenium conducted in THF afforded the SiSe 2 complex (bis-NHC)Si(=Se)Se!GaCl 3 3.Remarkably,the reaction of 1 with Te=P(nBu) 3 as agentle Te transfer reagent led to the isolation of the monomeric SiTe 2 complex (bis-NHC)SiTe 2 4,t he first structurally characterized Lewis acid free heavy CO 2 homologue complex. The isolated compounds 2, 3,and 4 have been fully characterized,i ncluding single-crystal X-ray diffraction analyses.T heir electronic structures and spectroscopic data have also been studied by quantum-chemical calculations.Carbonmonoxide,CO, featuring amonomeric structure and Angewandte Chemie Communications 6299

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Section: Communicationsmentioning

confidence: 99%

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Taming Silicon Congeners of CO and CO₂: Synthesis of Monomeric Si^II and Si^IV Chalcogenide Complexes

et al. 2017

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“…Complexes 6 , 7a , 8a , and 10 represent the first examples of isolable monomeric SiX 2 complexes. Recently, molecular Si 2 X 4 (X = O, S, Se) complexes, representing dimers of SiX 2 supported by NHCs or cAACs, have been reported by the Robinson and Roesky groups, starting from zerovalent disilicon complexes. − …”

Section: Reactivity Of Silylone Toward Elemental Chalcogensmentioning

confidence: 99%

A New Area in Main-Group Chemistry: Zerovalent Monoatomic Silicon Compounds and Their Analogues

2017

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Monoatomic zerovalent main-group element complexes emerged very recently and attracted increasing attention of both theoretical and experimental chemists. In particular, zerovalent silicon complexes and their congeners (metallylones) stabilized by neutral Lewis donors are of significant importance not only because of their intriguing electronic structure but also because they can serve as useful building blocks for novel chemical species. Featuring four valence electrons as two lone pairs at the central atoms, such complexes may form donor-acceptor adducts with Lewis acids. More interestingly, with the central atoms in the oxidation state of zero, they could pave a way to new classes of compounds and functional groups that are otherwise difficult to realize. In this Account, we mainly describe our contributions in the chemistry of monatomic zerovalent silicon (silylone) and germanium (germylone) supported by a chelate bis-N-heterocyclic carbene (bis-NHC) ligand in the context of related species developed by other groups in the meantime. Utilizing the bis-NHC stabilized chlorosilyliumylidene [:SiCl] and chlorogermyliumylidene [:GeCl] as suitable starting materials, we successfully isolated silylone (bis-NHC)Si and germylone (bis-NHC)Ge, respectively. The electronic structures of the latter complexes established by theoretical calculations and spectroscopic data revealed that they are genuine metallylone species with electron-rich silicon(0) and germanium(0) centers. Accordingly, they can react with 1 molar equiv of GaCl to form Lewis adducts (bis-NHC)E(GaCl) (E = Si, Ge) and with 2 molar equiv of ZnCl to furnish (bis-NHC)Si(ZnCl). Conversion of the metallylones with elemental chalcogens affords isolable monomeric silicon(II) and germanium(II) monochalcogenides (bis-NHC)EX(GaCl) (X = Se, Te), representing molecular heavier congeners of CO. Moreover, their reaction with elemental chalcogens can also yield monomeric silicon(IV) and germanium(IV) dichalcogenides (bis-NHC)EX (X = S, Se, Te) as the first isolable complexes of the molecular congeners of CO. Moreover, (bis-NHC)Si could even activate CO to afford the monomolecular silicon dicarbonate complex (bis-NHC)Si(CO) via the formation of SiO and SiO complexes as intermediates. Furthermore, starting with a chelate bis-N-heterocyclic silylene supported [:GeCl], we developed two bis-N-heterocyclic silylene stabilized germylone→Fe(CO) complexes. Our achievements in the chemistry of metallylones demonstrate that the characteristic of monatomic zerovalent silicon and its analogues can provide novel reaction patterns for access to unprecedented species and even extends the series of functional groups of these elements. With this, we can envision that more interesting zerovalent complexes of the main-group elements with unprecedented reactivity will follow in the near future.

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“…Moreover, heavier analogues of CO 2 were synthesized in several instances. For example, a dimeric SiSe 2 unit was stabilized by a cyclic alkyl(amino)carbene (cAAC) . Additionally, the use of a donor–acceptor imino phosphorene ligand and an additional base coordination allowed for the synthesis of SiO 2 complex H that contains a SiO 2 unit comprising a very short and a long Si–O bond .…”

Section: Introductionmentioning

confidence: 99%

Reactions of a Silicon-Based Cyclic Silylone with Chalcogens

et al. 2019

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Tetrasilasilylone N is composed of a silicon(0) atom, two NHC-coordinated silylenes, and a silaimine (SiN) group. It reacts rapidly and selectively with the chalcogens selenium and tellurium to afford corresponding dichalcogenides 1 and 2 in high yields of 69–79%. In these compounds, one chalcogen atom is connected to the silicon(0) atom with a short bond in the range of SiE double bonds. The second chalcogen atom adopts the bridging position between the Si(0) atom and the SiN group. Using only 1 equiv of tellurium affords the selective formation of monotelluride 3 in 84% yield. In this monotelluride, the tellurium atom adopts a bridging position between the silylone functionality and the SiN group.

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A soluble molecular variant of the semiconducting silicondiselenide

Abstract: Silicondiselenide is a semiconductor and exists as an insoluble polymer (SiSe2)n which is prepared by reacting elemental silicon with selenium powder in the temperature range of 400–850 °C.

Cited by 36 publications

References 31 publications

Taming Silicon Congeners of CO and CO₂: Synthesis of Monomeric Si^II and Si^IV Chalcogenide Complexes

Taming Silicon Congeners of CO and CO₂: Synthesis of Monomeric Si^II and Si^IV Chalcogenide Complexes

A New Area in Main-Group Chemistry: Zerovalent Monoatomic Silicon Compounds and Their Analogues

Reactions of a Silicon-Based Cyclic Silylone with Chalcogens

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A soluble molecular variant of the semiconducting silicondiselenide

Abstract: Silicondiselenide is a semiconductor and exists as an insoluble polymer (SiSe2)n which is prepared by reacting elemental silicon with selenium powder in the temperature range of 400–850 °C.

Cited by 36 publications

References 31 publications

Taming Silicon Congeners of CO and CO2: Synthesis of Monomeric SiII and SiIV Chalcogenide Complexes

Taming Silicon Congeners of CO and CO2: Synthesis of Monomeric SiII and SiIV Chalcogenide Complexes

A New Area in Main-Group Chemistry: Zerovalent Monoatomic Silicon Compounds and Their Analogues

Reactions of a Silicon-Based Cyclic Silylone with Chalcogens

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Taming Silicon Congeners of CO and CO₂: Synthesis of Monomeric Si^II and Si^IV Chalcogenide Complexes

Taming Silicon Congeners of CO and CO₂: Synthesis of Monomeric Si^II and Si^IV Chalcogenide Complexes