Synthesis and Properties of 1,2-Dichlorodisilane and 1,1,2-Trichlorodisilane

Gupper, Andreas; Haßler, Karl

doi:10.1002/1099-0682(200108)2001:8<2007::aid-ejic2007>3.0.co;2-2

Cited by 13 publications

(3 citation statements)

References 35 publications

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“…All chemical shifts and coupling constants were consistent with the proposed structures. Furthermore, excellent agreement with literature data of open-chained hydrosilanes containing aryl or chloro substituents was observed. ,,, The −arylSiH– and −ClSiH– resonances exhibit doublet splitting and characteristic low-field shifts relative to the triplets arising from the endocyclic −SiH 2 – groups. The exceptionally large value of 1 J ( 29 Si– 1 H) = 231.3 Hz observed for the −SiHCl group in 1 is typical for silicon hydrides bearing electronegative substituents .…”

Section: Resultssupporting

confidence: 85%

Partial Halogenation of Cyclic and Branched Perhydropentasilanes

et al. 2012

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The perhydropentasilanes (H(3)Si)(4)Si and Si(5)H(10) were chlorinated with SnCl(4) to give chlorohydropentasilanes without destruction of the Si-Si backbone. Tetrachloroneopentasilane (ClH(2)Si)(4)Si (2) was prepared in high yield from (H(3)Si)(4)Si and 3.5 equiv of SnCl(4), while Si(5)H(10) and an equimolar amount of SnCl(4) afforded a mixture of ∼60% of ClSi(5)H(9) (1) with polychlorinated cyclopentasilanes and unreacted starting material, which could not be separated by distillation. The selective monochlorination of Si(5)H(10) was achieved starting from MesSi(5)Cl(9) (3; Mes = 2,4,6-trimethylphenyl) or TBDMP-Si(5)Cl(9) (4; TBDMP = 4-tert-butyl-2,6-dimethylphenyl). 3 or 4 was successfully hydrogenated with LiAlH(4) to give MesSi(5)H(9) (6) or TBDMP-Si(5)H(9) (7), which finally gave 1 along with aryl-H and Si(5)H(10) after treatment with an excess of liquid anhydrous HCl. All compounds were characterized by standard spectroscopic techniques. For Si-H derivatives, the coupled (29)Si NMR spectra were analyzed in detail to obtain an unequivocal structural assignment. The molecular structures of 2-4 were further confirmed by X-ray crystallography.

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Section: Resultssupporting

confidence: 85%

Partial Halogenation of Cyclic and Branched Perhydropentasilanes

et al. 2012

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“…29 Si NMR parameters of the polysilanyl hydrides 9 − 13 and 16 − 20 are summarized in Table . Excellent agreement with literature data obtained for amino- and chloro-containing di-, tri-, and tetrasilanes is observed. , The −SiH 2 NR 2 and −SiH 2 Cl resonances, respectively, exhibit the characteristic low-field shifts relative to the −SiH 3 and to the −SiH 2 − signals. Typical values for 1 J ( 29 Si− 1 H) are observed; the increased coupling constants within the −SiH 2 NR 2 and −SiH 2 Cl groups are typical for silicon hydrides bearing electronegative substituents.…”

Section: Resultssupporting

confidence: 88%

Linear and Cyclic Polysilanes Containing the Bis(trimethylsilyl)amino Group: Synthesis, Reactions, and Spectroscopic Characterization

2003

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The reaction of linear (Si(n)Cl(2)(n)(+2); n = 3-5) and cyclic (Si(5)Cl(10)) perchloropolysilanes with 1 or 2 equiv of LiN(SiMe(3))(2) results in the formation of the bis(trimethylsilyl)amino derivatives (Me(3)Si)(2)NSi(3)Cl(7) (1), (Me(3)Si)(2)NSi(4)Cl(9) (2), (Me(3)Si)(2)N(SiCl(2))(n)N(SiMe(3))(2) (n = 3, 4; n = 4, 5; n = 5, 6), cyclo-(Me(3)Si)(2)NSi(5)Cl(9) (7), and cyclo-[(Me(3)Si)(2)N](2)Si(5)Cl(8) (8). 1-8 easily can be hydrogenated with LiAlH(4) to give the corresponding amino and diamino polysilanyl hydrides. The monosubstituted and cyclic compounds 1, 2, 7, and 8 additionally afford Si-Si bond scission products, which cannot be separated in all cases. Chloro- and dichloro derivatives of Si(3)H(8), n-Si(4)H(10), and n-Si(5)H(12) are obtained from the corresponding aminosilanes and dry HCl. All compounds were characterized by standard spectroscopic techniques. For Si-H derivatives the coupled (29)Si NMR spectra were analyzed to obtain an unequivocal structural proof.

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“…Arylsilanes with bulky aryl groups have been synthesized from the corresponding aryl-lithium reagents and silicon halides (including trichlorosilane) followed by hydride reduction. − Selectivity is only satisfactory with few and large aryl groups. Ortho-disubstitution can be assisted by employing difunctional amines as auxiliary reagents which direct the metalation to positions adjacent to the first silyl group …”

Section: Introductionmentioning

confidence: 99%

Synthetic Pathways to Hydrogen-Rich Polysilylated Arenes from Trialkoxysilanes and Other Precursors

2002

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The use of tri(alkoxy)silanes (RO)3SiH, which have recently become commercially available in greater than research scale quantities (R = Me, Et), has been probed for the preparation of hydrogen-rich arylsilanes ArSiH3. It was found that the silylation of aryl-lithium or (in situ) aryl-Grignard reagents is followed by RO/H ligand redistribution and can lead to fully hydrogenated products in a one-pot reaction without employment of any additional metal hydride. After hydrolytic workup, the overall yields are between 20 and 30%. Silane gas and tetra(alkoxy)silanes are the main byproducts. At an early stage of the reactions, the whole set of mixed-ligand silanes (RO)3 - n H n SiAr can be detected by GLC/MS techniques. Induced by the organometallic base, the reaction also includes aryl scrambling to give silanes Ar n SiH4 - n , Ar n Si(OR)4 - n , and Ar n Si(H/OR)4 - n . A reaction scheme is proposed that accounts for the product distribution. Examples are given for Ar = phenyl, 4-biphenylyl, 4,4‘-biphenyldiyl, 1-naphthyl, and 2-anisyl. The reaction gives only very poor yields of di(silyl)arenes. Silanes of this type were therefore prepared from (RO)3SiH compounds and the corresponding di(halo)arenes by the in situ Grignard procedure followed by LiAlH4 reduction. Representative cases are 1,2- and 1,4-di(silyl)benzene and 1,4-di(silyl)-2,5-dimethylbenzene. The primary reaction products 1,4-(EtO)3SiC6H4Si(OEt)3 and 1,4-[(EtO)3Si]2-2,5-(CH3)2C6H2 have been isolated, and the crystal structure of the latter was determined.

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Synthesis and Properties of 1,2-Dichlorodisilane and 1,1,2-Trichlorodisilane

Cited by 13 publications

References 35 publications

Partial Halogenation of Cyclic and Branched Perhydropentasilanes

Partial Halogenation of Cyclic and Branched Perhydropentasilanes

Linear and Cyclic Polysilanes Containing the Bis(trimethylsilyl)amino Group: Synthesis, Reactions, and Spectroscopic Characterization

Synthetic Pathways to Hydrogen-Rich Polysilylated Arenes from Trialkoxysilanes and Other Precursors

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