Predicted Siliconoids by Bridging Si9 Clusters through sp3-Si Linkers

Jantke, Laura‐Alice; Fässler, Thomas F.

doi:10.3390/inorganics6010031

Cited by 7 publications

(3 citation statements)

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“…, [19] were fully characterized by 1 Ha nd 29 Si NMR spectroscopy in solution.T he formation of well-defined solutions that contain nine-atom silicon clusters after activation with liquid ammonia finally paved the way for further conversionso ft hese clusters in solution with appropriate reactants. Theoretical studies support the formation of siliconoids by the attachment of sp 3 -Si linkers, [20] and triggered us to investigate the reactivity of Si 9 4À clusters obtained from K 12 Si 17 and chloro-silanes with the ambition to synthesize larger siliconoid units. The experimental resultsare supported by computational methods (DFT-PBE0/TZVP level of theory).…”

Section: àmentioning

confidence: 99%

Anionic Siliconoids from Zintl Phases: R₃Si₉⁻ with Six and R₂Si₉²⁻ with Seven Unsubstituted Exposed Silicon Cluster Atoms (R=Si(tBu)₂H)

Schiegerl

Karttunen

Klein

et al. 2018

Chemistry A European J

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Neutral and anionic silicon clusters (siliconoids) are regarded as important model systems for bulk silicon surfaces. For 25 years their formation from binary alkali metal silicide phases has been proposed, but experimentally never realized. Herein the silylation of a silicide, leading to the anionic siliconoids (Si(tBu)2H)3Si9− (1 a) and (Si(tBu)2H)2Si92− (2 a) with the highest known number of ligand‐free silicon atoms is reported for the first time. The new anions are obtained in a one‐step reaction of K12Si17/NH3(liq.) and Si(tBu)2HCl/THF. Electrospray ionization spectrometry and 1H, 13C, 29Si, as well as 29Si‐HMBC (heteronuclear multiple bond correlation) NMR spectroscopy, confirm the attachment of three silyl groups at a [Si9]4− cluster under formation of 1 a, in accordance with calculated NMR shifts. During crystal growth the siliconoid di‐anion 2 a is formed. The single‐crystal X‐ray structure determination reveals that two silyl groups are connected to the deltahedral Si9 cluster core, revealing seven unsubstituted exposed silicon cluster atoms with a hemispheroidal coordination. The negative charges −1 and −2 are delocalized over the six and seven siliconoid Si atoms in 1 a and 2 a, respectively.

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Section: àmentioning

confidence: 99%

Anionic Siliconoids from Zintl Phases: R₃Si₉⁻ with Six and R₂Si₉²⁻ with Seven Unsubstituted Exposed Silicon Cluster Atoms (R=Si(tBu)₂H)

Schiegerl

Karttunen

Klein

et al. 2018

Chemistry A European J

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“…55 Furthermore, theoretical studies suggest the formation of siliconoids with Si 9 4À units by the attachment of sp 3 -Si linkers. 56 Just recently, we used Si 9 clusters from the precursor K 12 Si 17 for the production of the anionic siliconoids (SiH t Bu 2 ) 3 Si 9 À (3a) and (SiH t Bu 2 ) 2 Si 9 2À (3b, Fig. 1d) via direct ligand attachment.…”

Section: Introductionmentioning

confidence: 99%

Silicon clusters with six and seven unsubstituted vertices via a two-step reaction from elemental silicon

et al. 2019

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“…Several articles comprising this issue focus on molecular silicon clusters and silicon surface chemistry. Jantke and Fässler report computational investigations on polymeric Si 9 clusters [10]. The stability and electronic nature of the related polymeric and oligomeric clusters are discussed.…”

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confidence: 99%

Coordination Chemistry of Silicon

Inoue¹

2019

Inorganics

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It is with great pleasure to welcome readers to this Special Issue of Inorganics, devoted to "Coordination Chemistry of Silicon". Investigations into silicon compounds continue to afford a wealth of novel complexes, with unusual structures and brand-new reactivities. In fact, the ongoing quest for silicon complexes with novel properties has led to a large number of silicon compounds, that contain various types of ligands or substituents. Use of the divergent coordination behavior of silicon to construct sophisticated low-and hyper-valent silicon complexes makes it possible to change their electronic structures and properties. Therefore, progress of the coordination chemistry of silicon can be the key concept for the design and development of next generation silicon compound-based applications. This Special Issue is associated with the most recent advances in coordination chemistry of silicon with transition metals, as well as main group elements, including the stabilization of low-valent silicon species through the coordination of electron-donor ligands, such as N-heterocyclic carbenes (NHCs) and their derivatives [1,2]. This Special Issue is also dedicated to the development of novel synthetic methodologies, structural elucidations, bonding analyses, and possible applications in catalysis or chemical transformations, using related organosilicon compounds [3]. Besides, recent years have witnessed great research efforts in silicon-based polymer chemistry, as well as silicon surface chemistry, which have become increasingly important for unveiling the correlations between nanoscopic structural features and macroscopic material properties, including the coordination behavior at silicon.The 19 articles composing this Special Issue can be considered as a representative selection of the current research on this topic, reflecting the diversity of silicon chemistry and yield an impressive compilation.Intrinsic coordination behaviors of silanes towards transition metals are the subject of several articles in this issue. For example, Nakata et al. discuss the synthesis and structure of a hydrido platinum(II) complex with a dihydrosilyl ligand that bears a bulky 9-triptycyl group [4]. The ligand exchange reaction of this mononuclear (hydrido)(dihydrosilyl) complex with various phosphines has also been studied. Sunada and coworkers provide an elegant method for accessing planar tetrapalladium clusters starting from octa(isopropyl)cyclotetrasilane through the insertion of palladium atoms into the Si-Si bonds of the cyclotetrasilane [5]. While the ligand exchange reaction with NHCs yields the more coordinatively unsaturated cluster, reaction with a trimethylolpropane phosphite affords a planar tripalladium cluster. Wagler and coworkers demonstrate a striking coordination chemistry of (2-pyridyloxy)silanes with transition metals (Pd, Cu) [6]. The molecular structures of the complexes have been elucidated by crystallographic analysis, and further computational investigations provided an in-depth understanding of the interatomic ...

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Predicted Siliconoids by Bridging Si9 Clusters through sp3-Si Linkers

Cited by 7 publications

References 56 publications

Anionic Siliconoids from Zintl Phases: R₃Si₉⁻ with Six and R₂Si₉²⁻ with Seven Unsubstituted Exposed Silicon Cluster Atoms (R=Si(tBu)₂H)

Anionic Siliconoids from Zintl Phases: R₃Si₉⁻ with Six and R₂Si₉²⁻ with Seven Unsubstituted Exposed Silicon Cluster Atoms (R=Si(tBu)₂H)

Silicon clusters with six and seven unsubstituted vertices via a two-step reaction from elemental silicon

Coordination Chemistry of Silicon

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Predicted Siliconoids by Bridging Si9 Clusters through sp3-Si Linkers

Cited by 7 publications

References 56 publications

Anionic Siliconoids from Zintl Phases: R3Si9− with Six and R2Si92− with Seven Unsubstituted Exposed Silicon Cluster Atoms (R=Si(tBu)2H)

Anionic Siliconoids from Zintl Phases: R3Si9− with Six and R2Si92− with Seven Unsubstituted Exposed Silicon Cluster Atoms (R=Si(tBu)2H)

Silicon clusters with six and seven unsubstituted vertices via a two-step reaction from elemental silicon

Coordination Chemistry of Silicon

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Anionic Siliconoids from Zintl Phases: R₃Si₉⁻ with Six and R₂Si₉²⁻ with Seven Unsubstituted Exposed Silicon Cluster Atoms (R=Si(tBu)₂H)

Anionic Siliconoids from Zintl Phases: R₃Si₉⁻ with Six and R₂Si₉²⁻ with Seven Unsubstituted Exposed Silicon Cluster Atoms (R=Si(tBu)₂H)