Synthesis, Structure, and Photolysis of Germatetrasilacyclopentanes

Suzuki, Hideo; Tanaka, Ken; Yoshizoe, Bin; Yamamoto, Tsuyoshi; Kenmotsu, Nozomu; Matuura, Syu; Akabane, Tohru; Watanabe, Hamao; Goto, Midori

doi:10.1021/om9804374

Cited by 14 publications

(11 citation statements)

References 50 publications

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“…Synthesis of 1‐Cyclohexyl‐2,2,3,3,4,4,5,5‐octaisopropyl‐1‐aza‐2,3,4,5‐tetrasilacyclopentane (4a): This compound was synthesized by a method similar to that used for 3a [Scheme , (c)], by treatment of 1,4‐dichloro‐1,1,2,2,3,3,4,4‐octaisopropylcyclotetrasilane11 Cl(R 2 Si) 4 Cl (R = i Pr; 1.4 g, 2.6 mmol) with lithium cyclohexylamide, prepared from cyclohexylamine (0.9 mL, 7.9 mmol in 5 mL of THF) and butyllithium (6.5 mL, 10.2 mmol in hexane). Compound 4a (recrystallized from 2‐propanol): 0.51 g, 35% yield; m.p.…”

Section: Methodsmentioning

confidence: 99%

“…Synthesis of 2,2,3,3,4,4,5,5‐Octaisopropyl‐1‐oxa‐2,3,4,5‐tetrasilacyclopentane 6a: This compound was synthesized by a method similar to that used for 5b , by hydrolysis of 1,4‐dichlorooctaisopropyltetrasilane11 Cl(R 2 Si) 4 Cl (R = i Pr; 1.02 g, 1.9 mmol) with H 2 O (3 mL) in THF (7 mL) at 50−60 °C for 15 h. Compound 6a (recrystallized from methanol/ethanol): 0.88 g, 96% yield; m.p. 308−315 °C.…”

Section: Methodsmentioning

confidence: 99%

“…We have previously studied some properties of various peralkylated cyclosilanes [R 1 R 2 Si] n ( n = 3−7)7 and have also reported preliminary results for [R 2 Si] 3 O 8. Recently, we described the synthesis, molecular structure, and photolysis of the [R 2 Si] n GeR′ 2 series [ n = 2: R = t BuCH 2 , R′ = Me 3 SiCH 2 ;9 n = 3: R = i Pr, t BuCH 2 , R′ = Me 3 SiCH 2 ( C , D );10 and n = 4: R = i Pr, t BuCH 2 , R′ = Me 3 SiCH 2 , Ph ( G − I )11].…”

Section: Introductionmentioning

confidence: 99%

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Peralkylated Four- and Five-Membered Cyclosilanes Containing a Heteroatom: Synthesis, Structure, and Properties

Watanabe

Suzuki

Takahashi

et al. 2002

Eur. J. Inorg. Chem.

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Seventeen peralkylated four-and five-membered heteroatom-containing silacycles [R 1 R 2 Si] n X [R 1 = iPr and/or R 2 = tBuCH 2 ; n = 3; X = CH 2 (1a, 1b), NR 3 (R 3 = C 6 H 11 ) (3a−d), O (5a−c), and n = 4; X = CH 2 (2a, 2b), NR 3 (R 3 = C 6 H 11 or Pr) (4a−d), and O (6a, 6b)] have been synthesized and characterized. The structural features of twelve compounds − 1b, 3a−d, and 5b (Si 3 X) and 2a, 4a−c, 6a, and 6b (Si 4 X) − determined by X-ray analysis have been investigated and geometrical differences between the silacycles bearing neopentyl groups and those with isopropyl groups as bulky substituents on silicon atoms have been identified. The ring strain energies for the compounds [R 2 Si] n X [n = 3, 4; R = Me, iPr; X = CH 2 , N(iPr), NMe, O, SiH 2 ], estimated by theoretical calculations at the PM3 level, are discussed in relation to experimentally ascertained structural features of the silacycles [R 2 Si] n X (n = 3, 4; R = iPr; X = CH 2 , NC 6 H 11 , O, SiR 2 ). 29 Si NMR spectra for 1−6 showed that the resonances for the α-silicon atoms attached to the heteroatoms X in the two ring-size series were shifted downfield by a deshielding effect due to an electronegative atom X; larger electronegativity (En) of X caused this effect at lower field. The chemical shifts of the Si α atoms showed a good linear correlation with the electronegativities of the heteroatoms X in the [R 2 Si] n X cycles. In the UV spectra for 1−6, little difference in [a] the longest-wavelength absorption (LWA) maxima was observed for [(iPr) 2 Si] n X and [(tBuCH 2 ) 2 Si] n X of the same ring size. The LWA bands for 1−6 and related compounds could be roughly classified into four groups: (a) [R 2 Si] 3 X (X = SiR 2 , GeRЈ 2 ) λ = 286−300 nm; (b) [R 2 Si] 3 X (X = CH 2 , NR 3 , O) (1, 3, 5), λ = 230−250 nm; (c) [R 2 Si] 4 X (X = SiR 2 , GeRЈ 2 ) λ = 274−280 nm; (d) [R 2 Si] 4 X (X = CH 2 , NR 3 , O) (2, 4, 6), λ = 250−260 nm. With the aid of the ionization potentials and the transition energies (E T ), the HOMO and LUMO levels for the series of compounds and the related ones were experimentally evaluated. The HOMO and LUMO levels thus obtained for [R 2 Si] 3 X and [R 2 Si] 4 X (R = iPr and tBuCH 2 ; X = SiR 2 , GeRЈ 2 , CH 2 , NC 6 H 11 , O) are discussed in terms of the calculated values and frontier orbitals on the basis of PM3 levels. The theoretical prediction for bond scission in the silacycles [(iPr) 2 Si] n X (n = 3, 4; X = CH 2 , NMe, O) in which the HOMOs and LUMOs have Si−Si bonding and antibonding character, respectively, was corroborated by the good agreement with experimental results from photolysis of the silacycles [R 2 Si] n X (n = 3, 4; R = iPr and tBuCH 2 ; X = CH 2 , NC 6 H 11 , O), with bond scission occurring only at the Si−Si bonds, and not at the Si−X bonds.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Peralkylated Four- and Five-Membered Cyclosilanes Containing a Heteroatom: Synthesis, Structure, and Properties

Watanabe

Suzuki

Takahashi

et al. 2002

Eur. J. Inorg. Chem.

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“…The photochemistry of catenated group 14 compounds is of interest since this method can be used to convert one type of catenate to another and also can be used for the generation of reactive intermediates including silylenes, germylenes, stannylenes, and group 14 element centered radical species that can be trapped and characterized . In the case of germanium, the photochemistry of the cyclotrigermane (Mes 2 Ge) 3 has been the most extensively studied and it has been shown that this compound is photochemically converted to a germylene Mes 2 Ge : and a digermene Mes 2 Ge=GeMes 2 .…”

Section: Introductionmentioning

confidence: 99%

Photodecompostion of the Oligogermanes nBu3GeGePh2GenBu3 and nBu3GeGePh3: Identification of the Photoproducts by Spectroscopic and Spectrometric Methods

et al. 2016

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The oligogermane nBu 3 GeGePh 2 GenBu 3 was photolyzed using UV-C light in the presence of acetic acid as a trapping agent and the photoproducts were identified using 1 H NMR spectroscopy, gas chromatography/electron-impact mass spectrometry, and high resolution accurate mass mass spectrometry. The products identified were the germanes nBu 3 GeH, nBu 3 GeOAc, and Ph 2 Ge(H)OAc (OAc = C 2 H 3 O 2 ) and the diger- [a]

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“…The germadisilaoxetane heterocycle is somewhat deformed with the following bond distances and endocyclic angles: Si-Ge 2. The five-membered germatetrasilacyclopentane ring systems of compounds 23 (R-Pr, f BuCH 2 ) [40,41] were characterized by X-ray analysis. The GeSi 4 heterocycle of these compounds forms an envelope (R-Pr) and a distorted half-chair conformations (R-BuCH 2 ).…”

mentioning

confidence: 99%

MOLECULAR STRUCTURE OF ORGANOSILICON COMPOUNDS WITH Si-M (M = Ge, Sn, Pb, Ti, Zr, Hf) BONDS

Lukevics¹,

Pudova²

1999

Main Group Metal Chemistry

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The results of the structural investigations of the group 4 metal derivatives containing direct Si-Ge, Si-Sn, Si-Pb, Si-Ti, Si-Zr, Si-Hf bonds are summarized in the present review. IntroductionRecently we have published a comprehensive survey of data on the molecular structure of organosilicon compounds with silicon-silicon bonds [1], as a part of the structural investigations related to the silyl derivatives of the group 4 elements with Si-M bonds. Herein, we present a review concerning the molecular structure of germanium, tin, lead, titanium, zirconium, hafnium derivatives bearing silyl substituents at the metal atoms. Only a few structures with direct Si-M (M=Ge, Sn, Pb, Ti, Zr, Hf) bonds were studied 10 years ago. Now the interest in this area is becoming increasingly prominent and exciting progress has been made in the chemistry and structural characterization of silyl derivatives of group 4 metals.

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Synthesis, Structure, and Photolysis of Germatetrasilacyclopentanes

Cited by 14 publications

References 50 publications

Peralkylated Four- and Five-Membered Cyclosilanes Containing a Heteroatom: Synthesis, Structure, and Properties

Peralkylated Four- and Five-Membered Cyclosilanes Containing a Heteroatom: Synthesis, Structure, and Properties

Photodecompostion of the Oligogermanes nBu3GeGePh2GenBu3 and nBu3GeGePh3: Identification of the Photoproducts by Spectroscopic and Spectrometric Methods

MOLECULAR STRUCTURE OF ORGANOSILICON COMPOUNDS WITH Si-M (M = Ge, Sn, Pb, Ti, Zr, Hf) BONDS

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