Low-temperature structure of allyl silatrane

White, J. M.; Jones, Simon C.

doi:10.1107/s0108270199002371

Cited by 7 publications

(8 citation statements)

References 3 publications

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“…The other one is a pentacoordinate allyldifluorosilane with an azobenzene ligand which generally offers the possibility for allyl rearrangement (Scheme 3,top). Recently, the photochemically shifted hexacoordination of an allylfluorosilane and the subsequent allylation of the azobenzene moiety were reported by Kano et al (Scheme 3,bottom) [4]. Photochemical activation, however, may contribute to the ease of organyl shift reactions as we have recently shown [1a].…”

Section: Introductionmentioning

confidence: 88%

“…Till now, there are only two crystal structures of hypercoordinate allylsilanes. One of them represents the allylsilatrane molecule which can not undergo any intramolecular rearrangement reactions due to the lack of unsaturated C=X moieties [4]. The other one is a pentacoordinate allyldifluorosilane with an azobenzene ligand which generally offers the possibility for allyl rearrangement (Scheme 3,top).…”

Section: Introductionmentioning

confidence: 99%

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Syntheses of Allyl- and 3-Silylpropyl-substituted Salen-like Tetradentate Ligands via Hypercoordinate Silicon Complexes

Wagler

Roewer

2006

Zeitschrift Für Naturforschung B

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The reaction of allylchlorosilanes (AllSiCl3, AllSiPhCl2) with the tetradentate salen-like ligand 1, o-HO-p-MeO-C6H3-C(Ph)=N-(CH2)2-N=C(Ph)-C6H3-p-OMe-o-OH, yields pentacoordinate silicon complexes of an allyl-substituted ligand system (o-O-p-MeO-C6H3-C(Ph)=N-(CH2)2- N-C(Ph,All)-C6H3-p-OMe-o-O)SiR (2a: R = Ph, 3: R = Cl). The allyl shift step involved in the formation of 2a and 3 probably occurs via an intermediate hexacoordinate silicon complex. This reaction is diastereoselective. The missing diastereomer of 2 (2b) was prepared using an alternative synthesis route, which starts from the trimethylsilyl derivative of ligand 1 o-Me3SiO-p-MeO-C6H3-C(Ph)=N- (CH2)2-N=C(Ph)-C6H3-p-OMe-o-OSiMe3. The diastereomers of 2 obtained from modified reaction pathways give rise to suggestions about the mechanism of formation of these complexes. Further functionalization of the allyl-substituted ligand system of 3 was carried out by hydrosilylation with HSiCl3 to yield complex 4 (o-O-p-MeO-C6H3-C(Ph)=N-(CH2)2-N-C(Ph)[(CH2)3-SiCl3]- C6H3-p-OMe-o-O)SiCl.

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Section: Introductionmentioning

confidence: 88%

Section: Introductionmentioning

confidence: 99%

Syntheses of Allyl- and 3-Silylpropyl-substituted Salen-like Tetradentate Ligands via Hypercoordinate Silicon Complexes

Wagler

Roewer

2006

Zeitschrift Für Naturforschung B

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“…Phosphorylaminopropylsilatranes (134)(135)(136)(137)(138)(139)(140)(141)(142)(143)(144)(145) were systematically generated by nucleophillic substitution reaction of 2-chloro-1,3,2-dioxaphosphinanes and aminopropylsilatrane (Scheme 9) 88 The reaction was carried out in dichloromethane in the presence of triethylamine. The contents were added at 10 1C in about 1 h followed by constant stirring for 2-4 h at room temperature.…”

Section: Route 3: Reaction Of Silatrane With Suitable Reagent To Form...mentioning

confidence: 99%

“…136 The molecular structure of 1-allyl-2,8,9trioxa-5-aza-1-silabicyclo[3.3.3]undecane shows hyperconjugation between the C-Si bond and an allyl double bond. 137 The effect of different R groups on equatorial Si-O, Si-N and Si-C/X bond lengths is given in Table 14. All the silatranes can be divided into eight categories on the basis of their general structure for understanding variation in Si-N bonds, and conclusions drawn from the different categories is given below.…”

Section: Crystallographic Studiesmentioning

confidence: 99%

Silatranes: a review on their synthesis, structure, reactivity and applications

2011

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This critical review summarizes progress of the rapidly developing and very active field of silatrane chemistry. The first part of the review deals with general synthetic approaches used to synthesize different silatranes. The most interesting feature of silatranes, i.e., variation of Si-N bond length on the basis of the axial substituent of Si, and other structural features, are described in the second part with special emphasis on crystallographic and theoretical studies. It is followed by a discussion on the reactivity of various silatranes. Silatranes have now gained acceptance for a wide variety of applications which are summarized in the last section of review. Some of them have extensive interest due to their medical use to heal wounds or stimulate hair-growth (pilotropic activity), biological properties, pharmacological properties e.g. antitumor, anticancer, antibacterial, anti-inflammatory, fungicidal activity, stimulating effect in animal production and seed germination effects. The review focuses on the extended potential of silatranes in sol-gel processes, mesoporous zeotypes, atomic force microscopy, commercial products such as adhesion promoters, polymer formation and rubber compositions. This critical review will be helpful for general researchers, experts, advanced undergraduates and newcomers working on silatrane chemistry as this review presents greater emphasis on synthesis and characterization, structural properties, reactivity and applications of silatranes in the field of biology, material science, sol-gel chemistry, pharmaceutics, agriculture and medicine (311 references).

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“…In literature, there are not many reports concerning the structural aspects of 1 and its reactivity. The crystal structure of 1 was determined in low temperature, and its correlation to hyperconjugation between the Si-C σ-electrons and the C=C π-system was discussed [15]. Allylsilatrane was functionalized in catalytic hydrosilylation and hydrogermylation, as well as in non-catalytic hydrostannation [16].…”

Section: Introductionmentioning

confidence: 99%