Synthesis, structure, and reactivity of the permethylated decasilane (Me3Si)3SiSiMe2SiMe2SiMe3)3

Whittaker, Stephen M.; Brun, Mari Carmen; Cervantes‐Lee, Francisco; Pannell, Keith H.

doi:10.1016/0022-328x(95)00322-h

Cited by 42 publications

(44 citation statements)

References 11 publications

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“…Scheme 1 To gain a better understanding of the reaction in Scheme 1 we also studied the cleavage of the doubly branched polysilane 4. [13] Reaction of 4 with one equivalent of MeLi leads to cleavage of bond A [i.e., 4 behaves as a member of series 1, even though it possesses a (Me 3 Si) 3 Si fragment], producing the novel branched polysilyl anion 1 (Scheme 2). The structure of 1 was first assigned by isolating the expected trapping products (Me 3 Si) 3 SiMe 2 SiMe 2 Si-(Me 3 Si) 2 SiR (R ‫؍‬ tBuMe 2 Si, PhMe 2 Si, CH 3 OCH 2 ) when treated with tBuMe 2 SiCl, PhMe 2 SiCl and CH 3 OCH 2 Cl, respectively (see Experimental Section).…”

Section: Resultsmentioning

confidence: 99%

The Syntheses and Molecular Structure of a Branched Oligosilyl Anion with a Record of Nine Silicon Atoms and of the First Branched Oligosilyl Dianion

Apeloig¹,

Korogodsky²,

Bravo‐Zhivotovskii³

et al. 2000

Eur. J. Inorg. Chem.

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Section: Resultsmentioning

confidence: 99%

The Syntheses and Molecular Structure of a Branched Oligosilyl Anion with a Record of Nine Silicon Atoms and of the First Branched Oligosilyl Dianion

Apeloig¹,

Korogodsky²,

Bravo‐Zhivotovskii³

et al. 2000

Eur. J. Inorg. Chem.

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“…For example, reaction of LiMe with 7 and 10, respectively, generates after 2-3 days the highly air-and moisture-sensitive branched lithium silanides Li-18 [70,71] and Li-19 [72] ( Figure 4). Similarly, branched polysilane 21 [73] can be converted into Li-22 [74] in good yields ( Figure 5). Recently, Marschner developed an easy and cheap synthetic method that gives access to a wide variety of potassium silanides via the selective cleavage of a Si-Si bond with KOBu t in THF [75].…”

Section: Cores Spacers and Wingsmentioning

confidence: 97%

Polysilane Dendrimers

Krempner

2012

Polymers

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Abstract:The synthesis, structure and electronic properties of polysilane dendrimers, a relatively new class of highly branched and silicon-rich molecular architectures is reviewed. After a detailed discussion of main synthetic strategies to well-defined single-core and double-core polysilane dendrimers, important structural and conformational features determined by single crystal X-ray crystallography and 29 Si-NMR spectroscopy are presented. The last part highlights the most interesting photochemical properties of polysilane dendrimers such as UV absorption and emission behavior, which are compared with those of linear and branched polysilanes.

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“…The highly intensive band at 254 nm for 11 corresponds to the Si6 framework, and in this case, a weak hypercoordination results in weak hypsochromic shift compared to the all-methylated reference compound. 46 Furthermore, the effect of hypercoordination based on aminotrisphenols with terminal modification 17d is very weak.…”

Section: Results and Discussionmentioning

confidence: 99%

Hypercoordinated Oligosilanes Based on Aminotrisphenols

et al. 2018

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The hypercoordinated silicon chlorides ClSi[(o-OC6H4)3N] (3) and ClSi[(OC6H2Me2CH2)3N] (5) were used for the synthesis of catenated derivatives (Me3Si)3SiSi[(o-OC6H4)3N] (9), (Me3Si)3SiSiMe2SiMe2Si(SiMe3)2Si[(o-OC6H4)3N] (11), and (Me3Si)3SiSi[(OC6H2Me2CH2)3N] (13) in reactions with (Me3Si)3SiK·THF (7) or (Me3Si)3SiK·[18-crown-6] (8). It was found that the nature of the (Me3Si)3SiK solvate determines the product of interaction, resulting in the formation of (Me3Si)3Si(CH2)4OSi[(OC6H2Me2CH2)3N] (12) or 13. Compounds obtained were characterized using multinuclear NMR and UV–vis spectroscopy and mass spectrometry. The molecular structures of 3, 9, and 11–13 were investigated by single-crystal X-ray analysis, featuring hypercoordinated Si atoms in a trigonal-bipyramidal coordination environment with O atoms in the equatorial plane. The structure of the side product [N(CH2C6H2Me2O)3Si]2O (6) was also studied, indicating highly tetrahedrally distorted trigonal-bipyramidal environment at the Si atoms, which was confirmed by crystal density functional theory calculations indicating the very weak Si ← N interaction. The Si···N interatomic distances span a broad range (2.23–2.78 Å). The dependence of structural and NMR parameters for hypercoordinated catenated compounds from the type of the ligand was established.

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Synthesis, structure, and reactivity of the permethylated decasilane (Me3Si)3SiSiMe2SiMe2SiMe3)3

Cited by 42 publications

References 11 publications

The Syntheses and Molecular Structure of a Branched Oligosilyl Anion with a Record of Nine Silicon Atoms and of the First Branched Oligosilyl Dianion

The Syntheses and Molecular Structure of a Branched Oligosilyl Anion with a Record of Nine Silicon Atoms and of the First Branched Oligosilyl Dianion

Polysilane Dendrimers

Hypercoordinated Oligosilanes Based on Aminotrisphenols

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