Facile synthesis and bridgehead-functionalization of bicyclo[3.3.3]pentasiloxanes

Yokouchi, Yuki; Ishida, Shintaro; Onodera, Tsunenobu; Oikawa, Hidetoshi; Iwamoto, Takeaki

doi:10.1039/c7cc08790j

Cited by 5 publications

(6 citation statements)

References 41 publications

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“…Compound 9 is a rare example of a tricyclic oligosiloxane. A somewhat related bicyclo[3.3.3]pentasiloxane was recently obtained by Iwamoto and co-workers using m CPBA oxidation of a 1,3-bis(trimethylsilyl)bicyclo[1.1.1]pentasilane . Compound 10 features a very simple 29 Si NMR spectrum with only two lines; the typical upfield resonances for the anionic silicon atoms (−186.7 ppm) are accompanied by a peak at 15.5 ppm for the Si O units.…”

Section: Resultsmentioning

confidence: 93%

“…The compound might be regarded as a building block for the synthesis of low dimensional materials such as one-dimensional nanorods consisting of bridgehead connected bicyclo[3.3.3]trisiloxane units. 37 …”

Section: Resultsmentioning

confidence: 99%

“…For this reason, we have prepared several different silylated siloxanes, and in doing so, disiloxane 1 (Scheme ) turned out to be an easily available ligand with great opportunities for further transformations, leading to a variety of interesting new compounds. Furthermore, theoretical , and synthetic aspects − of siloxanes have gained considerable attraction in recent times. Despite the large structural variety of oligosilanes that have been prepared over the past years, compounds with Si–Si bonds and Si-O-Si units are not very abundant.…”

Section: Introductionmentioning

confidence: 99%

“…A somewhat related bicyclo [3.3.3]pentasiloxane was recently obtained by Iwamoto and co-workers using mCPBA oxidation of a 1,3-bis(trimethylsilyl)bicyclo[1.1.1]pentasilane. 37 Compound 10 features a very simple 29 Si NMR spectrum with only two lines; the typical upfield resonances for the anionic silicon atoms (−186.7 ppm) are accompanied by a peak at 15.5 ppm for the SiO units. The compound might be regarded as a building block for the synthesis of low dimensional materials such as one-dimensional nanorods consisting of bridgehead connected bicyclo [3.3.3]trisiloxane units.…”

Section: ■ Introductionmentioning

confidence: 99%

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Chemistry of a 1,5-Oligosilanylene Dianion Containing a Disiloxane Unit

2019

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Synthesis of a number of disiloxane containing cyclo- and bicyclooligosilanes is described starting from the dipotassium 1,5-oligosiloxanylene diide derived from 1,3-bis[tris(trimethylsilyl)silyl]tetramethyldisiloxane. In addition, the use of this particular fragment as ligand for zinc and group 4 metallocene complexes was studied. Both types of compounds exhibit marked structural differences compared to related compounds containing Si-Si-Si units instead of the Si-O-Si fragment.

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Section: Resultsmentioning

confidence: 93%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Chemistry of a 1,5-Oligosilanylene Dianion Containing a Disiloxane Unit

2019

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“…As suggested by the angle–basicity correlation, their basicity will be substantially higher in comparison to the basicity of siloxane units incorporated into chains and consequently they have different material properties . Hence, the coordination chemistry of cyclic siloxanes has been the focus of much recent research …”

Section: Introductionmentioning

confidence: 99%

Covalency and Ionicity Do Not Oppose Each Other—Relationship Between Si−O Bond Character and Basicity of Siloxanes

Fugel

Hesse

Pal

et al. 2018

Chemistry A European J

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Covalency and ionicity are orthogonal rather than antipodal concepts. We demonstrate for the case of siloxane systems [R Si-(O-SiR ) -O-SiR ] that both covalency and ionicity of the Si-O bonds impact on the basicity of the Si-O-Si linkage. The relationship between the siloxane basicity and the Si-O bond character has been under debate since previous studies have presented conflicting explanations. It has been shown with natural bond orbital methods that increased hyperconjugative interactions of LP(O)→σ*(Si-R) type, that is, increased orbital overlap and hence covalency, are responsible for the low siloxane basicity at large Si-O-Si angles. On the other hand, increased ionicity towards larger Si-O-Si angles has been revealed with real-space bonding indicators. To resolve this ostensible contradiction, we perform a complementary bonding analysis, which combines orbital-space, real-space, and bond-index considerations. We analyze the isolated disiloxane molecule H SiOSiH with varying Si-O-Si angles, and n-membered cyclic siloxane systems Si H O(CH ) . All methods from quite different realms show that both covalent and ionic interactions increase simultaneously towards larger Si-O-Si angles. In addition, we present highly accurate absolute hydrogen-bond interaction energies of the investigated siloxane molecules with water and silanol as donors. It is found that intermolecular hydrogen bonding is significant at small Si-O-Si angles and weakens as the Si-O-Si angle increases until no stable hydrogen-bond complexes are obtained beyond φ =168°, angles typically displayed by minerals or polymers. The maximum hydrogen-bond interaction energy, which is obtained at an angle of 105°, is 11.05 kJ mol for the siloxane-water complex and 18.40 kJ mol for the siloxane-silanol complex.

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A Clean One‐Pot Synthesis of Structurally Ordered Linear, Monocyclic, and Bicyclic Oligosiloxanes

Shinohara,

Hatori,

Yamashita

et al. 2024

Angewandte Chemie

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A highly selective cross‐coupling reaction between Si‐OAc (AcO = acetoxy) and Si‐OH compounds that generates unsymmetrical and symmetrical oligosiloxanes concurrent with the release of acetic acid has been developed. The high selectivity arises from the reactivity difference that depends on the varying number of acetoxy groups present, thus facilitating a clean one‐pot synthesis of oligosiloxanes. For instance, the reactions of di‐, tri‐, or tetraacetoxysilanes with silanols furnish acetoxy‐containing di‐ and trisiloxanes in high yield. Two equivalents of tetraacetoxysilane can react with various silanediols to form 1,1,1,3,3,3‐hexaacetoxytrisiloxanes, which subsequently react with a second molecule of a silanediol to selectively afford 1,1,3,3‐tetraacetoxycyclotetrasiloxanes. The cyclotetrasiloxanes further react with a third molecule of silanediol to provide unprecedented bicyclic pentasiloxanes with acetoxy groups at the bridgehead silicon atoms. Applications of the acetoxy‐containing products as efficient surface‐treatment agents and new building blocks for highly heat‐resistant materials are demonstrated.

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Facile synthesis and bridgehead-functionalization of bicyclo[3.3.3]pentasiloxanes

Cited by 5 publications

References 41 publications

Chemistry of a 1,5-Oligosilanylene Dianion Containing a Disiloxane Unit

Chemistry of a 1,5-Oligosilanylene Dianion Containing a Disiloxane Unit

Covalency and Ionicity Do Not Oppose Each Other—Relationship Between Si−O Bond Character and Basicity of Siloxanes

A Clean One‐Pot Synthesis of Structurally Ordered Linear, Monocyclic, and Bicyclic Oligosiloxanes

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