Hydrosilylation of ethynylsilanes with dimethyl(2-thienyl)silane

Lukevics, É.; Pudova, Olga; Sturkovich, R.; Gaukhman, A.

doi:10.1016/0022-328x(88)80129-3

Cited by 15 publications

(9 citation statements)

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“…The trimethylsilyl group again gives rise to a shift to a lower field but the magnitude of the influence is reversed compared to the phenyl group. [10] The tris(trimethylsilyl)silyl group has a similar but even more pronounced influence (Table 1). This plain increment system can also be used advantageously for a rough estimate of disubstituted alkynes, as seen from Table 2, where the observed 13 C shift values for the tris(trimethylsilyl)silylated alkynes can be compared to those obtained by simple increment addition to the base value of δ ϭ 71.9 ppm for acetylene.…”

Section: Nmr Spectroscopymentioning

confidence: 84%

“…The molecular structure and numbering of 6 with 30% probability thermal ellipsoids; all hydrogen atoms have been omitted for clarity; selected bond lengths (Å ) and bond angles (°) with estimated standard deviations: Si(1)ϪC(1) 1.835(3), Si(1)ϪSi (2) 2.3430 (15), Si(1)ϪSi (3) 2.3469 (16), Si(1)ϪSi (4) 2.3466(13), C(1)ϪC (1A) 1.217(6), C(1)ϪSi (1)ϪSi (2) 105.73(11), C(1)ϪSi(1)ϪSi(3) 104.79(11), Si(2)ϪSi(1)ϪSi (3) 113.33(6), C(1)ϪSi(1)ϪSi (4) 104.76(10), Si (2)ϪSi (1)ϪSi (4) 112.98(6), Si(3)ϪSi(1)ϪSi (4) 114.11(6), C(1)ϪSi(1)ϪSi (2)ϪC (4) 178.7(4), Si(1)ϪC(1)ϪC(1A) 178.9 (4) complete. Phenylacetylene derived compounds (3,10) are the most reactive among all investigated materials. Reaction with a compound possessing two alkynyl substituents (9) led to a vigorous and strongly colored reaction which did not yield soluble silicon containing material.…”

Section: Resultsmentioning

confidence: 99%

“…Increments for the calculation of 13 C NMR shifts of substituted alkynes [9,10,16] In the case of alkynylsilanes 13 C NMR spectroscopy is also of some interest. As acetylenes have only two substituents it is easy to study their influence on the 13 C NMR shift.…”

Section: Nmr Spectroscopymentioning

confidence: 99%

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Synthesis and Reactions of Alkynyl Oligosilanes

et al. 2004

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Synthesis, properties, and reactions of various alkynyl oligosilanes, and their potassium derivatives are described. A series of tris(trimethylsilyl)silylalkynes have been prepared. Their reaction with potassium tert‐butoxide leads to the corresponding potassium derivatives, which can be subjected to further derivatization. X‐ray structures of three oligosilylalkynes are reported. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Nmr Spectroscopymentioning

confidence: 84%

Section: Resultsmentioning

confidence: 99%

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Synthesis and Reactions of Alkynyl Oligosilanes

et al. 2004

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“…production of the mono-, di-, and triethynyl products from [8] PhSiH3 + HC=C + primary silanes (see Table 1) strongly suggest that the greater electron-withdrawing power of the ethynyl group compensates C=CH for its greater size relative to the H atom. On the other hand, the lower electronegativity and larger steric requirements of alkyl H 2 S i (~h ) C~C C 6 H 4 C C H + H2 groups are in accord with the low activity of dialkylsilanes and the extremely low reactivity of trialkylsilanes.…”

Section: Resultsmentioning

confidence: 99%

“…In two other cases, dehydrocoupling in low yield was found to accompany hydrosilation (8) and hydrogen transfer (9) reactions. In addition, acetylenes have been successfully coupled by copper(1) catalyzed oxidative coupling (lo), but there was no evidence that the coupling can be carried out in the absence of oxygen.…”

Section: Introductionmentioning

confidence: 99%

Copper(I) chloride catalyzed cross-dehydrocoupling reactions between silanes and ethynyl compounds. A new method for the copolymerization of silanes and alkynes

Liu¹,

Harrod²

1990

Can. J. Chem.

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In the presence of an amine, copper(1) chloride is an effective catalyst for the cross-dehycrocoupling of silanes with alkynes. The reactions proceed at useful rates above 100°C, but rates drop dramatically on going from lo to 2' to 3' organosilanes. Primary silanes, RSiH3 (R = Ph,n-hexyl), react in astepwisefashion with phenylacetylene to give the products RSiH3., (CCPh), (x = 1-3), each of which has been isolated and characterized. The secondary silanes RRiSiH2 (R = R' = Ph; R = Ph, R' = Me; R = n-Bu, R' = Me) also give mono-and diphenylethynyl products. The dehydrocoupling reaction has been applied to the synthesis of new polymers containing bothacetylene units and silicon atoms in the backbone. 1,3-Diethynylbenzene gives polymers of relatively high molecular weight (M, = lo4-lo5) with phenylsilane and phenylmethylsilane, but reactions of phenylmethyldiethynylsilane are too slow to give anything beyond low molecular weight oligomers.Key words: organosilanes, alkynes, dehydrocoupling, copper(1) chloride, polymers, catalysis.HUA QIN LIU et JOHN F. HARROD. Can. J. Chem. 68, 1 100 (1990).En prCsence d'une amine, le chlorure de cuivre(1) est un catalyseur efficace pour le dChydro-couplage croisC des silanes avec les alcynes. Les rCactions se produisent a des vitesses raisonnables lorsqu'on opere au-dessus de 100°C; toutefois, les vitesses diminuent d'une f a~o n dramatique lorsqu'on passe des organosilanes l o aux 2" et aux 3' . La rCaction des silanes primaires, RSiH3 (R = Ph, n-hexyle), avec le phCnylacCtylene se produit par Ctape pour donner les produits RSiH3, (CCPh), (x = 1-3); chacun de ces produits a CtC is016 et caractCrisC. Les silanes secondaires RR1SiH2 (R = R' = Ph; R = Ph, R' = Me; R = nBu, R' = Me) donnent aussi des produits mono-et di-phCnylCthynyles. On a appliquC la reaction de dthydro-couplage la synthbse de nouveaux polymeres dont la chaine fondamentale contient a la fois des unitCs acbtylbnes et des atomes de silicium. Avec le pEnylsilane et le phCnylmCthylsilane, le 1,3-diethynylbenzene fournit des polymkres de poids molCculaires relativement ClevCs (M, = lo4-lo5); toutefois, les rCactions du phCnylmCthyldiCthynylsilane sont tellement lentes que les seuls produits isolCs sont des oligombres de bas poids molCculaires.

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