A Route to a Germanium-Carbon Triple Bond: First Chemical Evidence for a Germyne

Bibal, Christine; Mazières, Stéphane; Gornitzka, Heinz; Couret, C.

doi:10.1002/1521-3773(20010302)40:5<952::aid-anie952>3.0.co;2-s

Cited by 63 publications

(13 citation statements)

References 28 publications

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“…Recent experimental work involving the photolysis of the diazo derivative ArGeC(N) 2 SiMe 3 (Ar = C 6 H 3 -2,6-(NMe 2 ) 2 ) in the presence of alcohols has shown that ArGe(OR) 2 CH 2 SiMe 3 could be obtained. 18 These results supported the view that the germyne species ArGeCSiMe 3 was probably generated as an intermediate that is trapped upon reaction with the alcohol. Stable germyne compounds related to this intermediate cannot be far in the future.…”

Section: Future Developmentssupporting

confidence: 59%

“…13 In addition to the computational results a number of experiments have indicated the existence of alkyne-like transient species such as MeSiSiMe, 14 17 HCSiX (X = F or Cl) or Me 3 SiCGeC 6 H 3 -2,6(CH 2 NPr i 2 ) 2 . 18 They were either detected spectroscopically or their existence was inferred on the basis of plausible reaction schemes. None has been isolated however.…”

Section: Introductionmentioning

confidence: 99%

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Silicon, germanium, tin and lead analogues of acetylenes

Power

2003

Chem. Commun.

206

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Recent experimental results which have described the characterization of the first, stable heavier group 14 element analogues of acetylenes are outlined. It is shown that the use of large terphenyl substituents allows the isolation of transition metal-heavier group 14 element complexes that can achieve essential triple bonding by a three-fold orbital interaction between the transition metal and group 14 moiety. On the other hand the alkyne analogues RMMR (R = Ge, Sn or Pb) display increasing distortions from linearity to trans-bent geometry due to the accumulation of non-bonding electron density at the group 14 element. The non-bonding electron density comes at the expense of electron density in the bonding region between the group 14 elements. Accordingly the bond orders are decreased to values that are near double for the germanium and tin derivatives and single for the lead compound.

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Section: Future Developmentssupporting

confidence: 59%

Section: Introductionmentioning

confidence: 99%

Silicon, germanium, tin and lead analogues of acetylenes

Power

2003

Chem. Commun.

206

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“…Many experimental and theoretical studies have been devoted to the chemistry of unsaturated compounds of the heavy group 14 elements, but very few compounds of the heteroacetylene (RCºMR¢) typei.e., molecules containing a triple bond between a carbon atom and a heavier atom have been synthesized and characterized, [1][2][3][4][5] presumably because of the high steric requirements and the reactivities of their polar C-M bonds. Although there have been several theoretical studies on these types of compounds, most have concerned carbon-silicon triple bonds.…”

Section: Introductionmentioning

confidence: 99%

“…We were stimulated into performing this insertion study by the recent observations of Sakamoto, Kira, and coworkers regarding the carbene-like reaction modes of stannynes (RCºSnR¢, R = Si(i-Pr) 3 , R¢ = 2,6-Tip 2 -C 6 H 3 ). 2 Due to some limitation in the basis set explained later, we switched our study to the insertion reactivity for the lighter XCºGeY compounds (X,Y=H, Cl and F).…”

Section: Introductionmentioning

confidence: 99%

Computational Studies on Insertion Reaction of Germynes

Cheng

Chu

2006

J Chinese Chemical Soc

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This paper describes theoretical studies on the insertion reaction of germynes XC ≡ GeY (X,Y=H, Cl and F) at the carbon site into a C‐H bond of CH4 performed at the QCISD(T)/6–311G*//QCISD/6–31G* level of theory. This work was inspired by the observation by Sakamoto, Kira, and coworkers on the carbene‐like reaction mode for stannyne (RC≡SnR′). Due to the limitation in the computation for the tin atom, the study was carried out on germyne compounds instead. We found that the valence state of the germyne moiety in the transition state and reaction product can be well represented by the triplet germyne. It has a bifunctional electronic structure of a triplet cabene joined to a singlet germylene (Structure 1).

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“…One year later, evidence of an intermediate germyne (Ge¸C) was also reported. 12 At this point it is germane to comment briefly on the chemistry of both germanium and tin. 2002 was a banner year for main group chemistry.…”

mentioning

confidence: 99%

Recent Developments in the Reactivity of Stable Disilynes

Asay

Sekiguchi

2012

Bulletin of the Chemical Society of Japan

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Unsaturated main group 14 species have unique properties and reactivity compared with their organic analogues. The isolation of stable disilynes, one of the most recent and intriguing additions to the catalog of unsaturated main group species, has opened the way for further studies into the differences between organic molecules and their heavy analogues. Since the isolation of the first disilyne, the reactivity and properties of these species has been the subject of numerous studies. Herein, the recent developments and results pertaining to the reactivity of disilynes are discussed.

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A Route to a Germanium-Carbon Triple Bond: First Chemical Evidence for a Germyne

Cited by 63 publications

References 28 publications

Silicon, germanium, tin and lead analogues of acetylenes

Silicon, germanium, tin and lead analogues of acetylenes

Computational Studies on Insertion Reaction of Germynes

Recent Developments in the Reactivity of Stable Disilynes

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