The isolation and x-ray crystal structure of Δ1,7 2,2,6,6-tetramethyl-4-thia-8,8-dimethyl-8-germabicyclo[5.1.0]octene; The first representative of germirenes

Egorov, Mikhail P.; Kolesnikov, S. P.; Struchkov, Yu. T.; Antipin, M. Yu.; Sereda, S. V.; Нефедов, О. М.

doi:10.1016/0022-328x(85)87302-2

Cited by 55 publications

(9 citation statements)

References 8 publications

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“…Although the number of structurally characterized germacyclopropenes 14,38,58−61 is rather small, the range of Ge–C bond lengths is surprisingly broad, ranging from 1.915 60 to 2.005 Å. 38 The value found for compound 11 is 1.958(2) Å, which is a rather typical Ge–C distance and is comparable to that of the related bis[tris(trimethylsilyl)silyl]germirene reported recently.…”

Section: Resultssupporting

confidence: 71%

Basic Reactivity Pattern of a Cyclic Disilylated Germylene

et al. 2016

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In order to estimate the reactivity of disilylated germylene phosphine adducts, a cyclic version of this compound class was reacted with a number of different reagents. Reactions with the chalcogens sulfur, selenium, and tellurium led to dimers of the heavy ketone analogues. Reactions with water and ethyl bromide proceeded to give the respective oxidized germanol and germyl bromide. Two different reactions with alkynes were observed which led either to a germacyclopropene, by addition of tolane to the germylene, or to a silagermacyclobutene, likely formed by addition of the alkyne across a silagermene. Reaction via the silagermene was also observed in the reaction with benzophenone. Reaction of a germylene phosphine adduct with GeCl2·(dioxane) provided insertion of the silylated germylene into a Ge–Cl bond, leading to a germylated chlorogermylene phosphine adduct.

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Section: Resultssupporting

confidence: 71%

Basic Reactivity Pattern of a Cyclic Disilylated Germylene

et al. 2016

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“…The aromaticity of HCPs should lead to a change in bond distances, in particular, to a lengthening of the CC bond and shortening of the C–E/M bonds. As was mentioned in the Introduction, this is the case for the 1Si and 1Ge molecules. ,, The computed and experimental structural data for 2 are given in Table .…”

Section: Resultsmentioning

confidence: 97%

“…In 1985 Egorov et al reported the synthesis of the germacyclopropene 1Ge ; they succeeded in purification of the substance by zone melting and isolating it as colorless crystals. The X-ray data obtained at −120 °C were as follows: the CGeC was angle 40.5°, the CC bond distance was 1.331 Å (a standard value for sp 2 –sp 2 bonds), and the C–Ge bond distances were shorter than the standard distance.…”

Section: Introductionmentioning

confidence: 96%

Aromaticity of 1-Heterocyclopropenes Containing an Atom of Group 14 or 4

2020

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The aromaticity of three-membered monoheterocycles containing a group 14 or 4 element was investigated by using modern aromaticity criteria: structural, electronic (FBO), optical (vibrational spectroscopy), energetic (ISE), and magnetic (NICS-scan, GIMIC). The results of all methods used show that the group 14 compounds are aromatic, with cyclopropene exhibiting σ aromaticity, whereas sila-and germacyclopropenes X 2 EC 2 R 2 exhibit pseudo-π aromaticity due to the interaction of the CC π bond orbital with the low-lying vacant antibonding σ* orbital of the X 2 E fragment (E = Si, Ge). At the same time, the results of MO and magnetic descriptor calculations testify against the aromaticity of group 4 cyclopropenes Cp 2 MC 2 R 2 (M = Ti, Zr, Hf). Thus, a fundamental dissimilarity in bonding schemes and electronic structure was disclosed between 1-heterocyclopropenes containing E = C, Si, Ge atoms and those containing M = Ti, Zr, Hf atoms, the latter molecules being in essence π complexes of acetylene.

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“…Silacyclopropenes 16 are thermally stable at ambient temperature; however only a few germacyclopropenes are known so far . This may be indicative that a germacyclopropene is far less stable than a silacyclopropene.…”

Section: Referencesmentioning

confidence: 99%

Synthesis and Properties of a Strained Germacycle Having a Ge−Ge Bond, 3,4-Benzo-1,1,2,2-tetraethyl-1,2-digermacyclobut-3-ene

et al. 1996

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A new strained germacycle, 3,4-benzo-1,1,2,2-tetraethyl-1,2-digermacyclobut-3-ene (1), was prepared by treatment of 1,2-bis(chlorodiethylgermyl)benzene with sodium in toluene. At ambient temperature, 1 was gradually oxidized in air to give 3,4-benzo-1,3-digerma-2-oxacyclopent-4-ene (2), and in the presence of sulfur, 1 was converted to 3,4-benzo-1,3-digerma-2-thiacyclopent-4-ene (3), quantitatively under similar thermal conditions. The digermacyclobutene 1 was thermally labile and readily underwent ring-opening polymerization in toluene to give the corresponding polymer 4 (M n = 4.4 × 105, M w = 7.4 × 105, M w/M n = 1.7). On thermolysis at 160 °C for 20 h, 1 gave two products, 4,5-benzo-1,2,3-trigermacyclopent-4-ene (5) and 3,4:6,7-dibenzo-1,2,5-trigermacyclohepta-3,6-diene (6), in reasonable yields. On the other hand, the thermolysis of 1 in the presence of phenylacetylene gave 2,3-benzo-1,4-digerma-5-phenyl-cyclohexa-2,5-diene (7), quantitatively. Further, 1 was thermolyzed in CCl4 to give two chlorinated products, 1,2-bis(chlorodiethylgermyl)benzene (9) and 1-(chlorodiethylgermyl)-2-(diethyl(trichloromethyl)germyl)benzene (10), in reasonable yields. The reaction mechanisms for the polymerization and the thermolysis are discussed.

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The isolation and x-ray crystal structure of Δ1,7 2,2,6,6-tetramethyl-4-thia-8,8-dimethyl-8-germabicyclo[5.1.0]octene; The first representative of germirenes

Cited by 55 publications

References 8 publications

Basic Reactivity Pattern of a Cyclic Disilylated Germylene

Basic Reactivity Pattern of a Cyclic Disilylated Germylene

Aromaticity of 1-Heterocyclopropenes Containing an Atom of Group 14 or 4

Synthesis and Properties of a Strained Germacycle Having a Ge−Ge Bond, 3,4-Benzo-1,1,2,2-tetraethyl-1,2-digermacyclobut-3-ene

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