Nachweis von HCSiF und HCSiCl als die ersten Moleküle mit formalen C≡Si-Bindungen

Karni, Miriam; Apeloig, Yitzhak; Schröder, Detlef; Zummack, Waltraud; Ragazzoni, Roberto; Schwarz, Helmut

doi:10.1002/(sici)1521-3757(19990201)111:3<343::aid-ange343>3.0.co;2-y

Cited by 27 publications

(1 citation statement)

References 37 publications

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“…The preparation and characterization of triply bonded heavier main group element (E 14 = Si, Ge, Sn, and Pb) molecules (i.e., RE 14 ≡E 14 R) is a popular field of study in inorganic chemistry [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 ]. From the valence electron viewpoint, the triply bonded RE 13 ≡E 15 R compound is isoelectronic to the RE 14 ≡E 14 R species.…”

Section: Introductionmentioning

confidence: 99%

Substituent Effects on the Stability of Thallium and Phosphorus Triple Bonds: A Density Functional Study

Mei

2017

Molecules

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Three computational methods (M06-2X/Def2-TZVP, B3PW91/Def2-TZVP and B3LYP/LANL2DZ+dp) were used to study the effect of substitution on the potential energy surfaces of RTl≡PR (R = F, OH, H, CH3, SiH3, SiMe(SitBu3)2, SiiPrDis2, Tbt (=C6H2-2,4,6-(CH(SiMe3)2)3), and Ar* (=C6H3-2,6-(C6H2-2, 4,6-i-Pr3)2)). The theoretical results show that these triply bonded RTl≡PR compounds have a preference for a bent geometry (i.e., ∠R⎼Tl⎼P ≈ 180° and ∠Tl⎼P⎼R ≈ 120°). Two valence bond models are used to interpret the bonding character of the Tl≡P triple bond. One is model [I], which is best described as TlP. This interprets the bonding conditions for RTl≡PR molecules that feature small ligands. The other is model [II], which is best represented as TlP. This explains the bonding character of RTl≡PR molecules that feature large substituents. Irrespective of the types of substituents used for the RTl≡PR species, the theoretical investigations (based on the natural bond orbital, the natural resonance theory, and the charge decomposition analysis) demonstrate that their Tl≡P triple bonds are very weak. However, the theoretical results predict that only bulkier substituents greatly stabilize the triply bonded RTl≡PR species, from the kinetic viewpoint.

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Section: Introductionmentioning

confidence: 99%

Substituent Effects on the Stability of Thallium and Phosphorus Triple Bonds: A Density Functional Study

Mei

2017

Molecules

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Combined Quantum Chemical and Mass Spectrometry Study of [Ge,C,H]+ and Its Neutral Counterpart

Jackson

Diefenbach

Schröder

et al. 1999

Eur. J. Inorg. Chem.

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The cation [Ge,C,H]+ has been generated by the electron ionisation of trichloromethylgermane. Collisional activation experiments were used to establish a Ge–C–H connectivity in this species, for which a significant fraction of the ion population was found to survive neutralisation‐reionisation mass spectrometry (NRMS) experiments. Thus, the neutral counterpart [Ge,C,H]0 is stable on a microsecond timescale. Becke's 3 parameter hybrid density functional (B3LYP) was used to map the ion and neutral potential‐energy surfaces, in conjunction with double‐zeta and triple‐zeta basis sets. The computational results obtained using the triple‐zeta basis sets suggest that, for the cation, the global minimum is the high spin 3Σ GeCH+, with the first Ge–C–H excited state, 1Σ GeCH+, approximately 39 kcal mol−1 less stable. The lowest energy ion structure with H–Ge–C connectivity is bent (3A′′HGeC+,∠H–Ge–C = 126.3) and 69 kcal mol−1 less stable than the global minimum. For the neutral, a doublet (2π) with Ge–C–H connectivity is predicted to be the global minimum. The classical barrier for the neutral 1,2‐hydrogen shift reaction on the doublet surface is negligible (0.1 kcal mol−1), while the smallest barrier for the cation is 13.0 kcal mol−1, corresponding to (3A′′) HGeC+ → (3Σ) GeCH+. Natural bond order analysis has been used to establish the order of the metal–carbon bond for selected states of both the neutral and the ion. Neutral and cationic isomers with Ge–C triple bonds were found to be high‐energy excited states, with the metal–carbon bonds in the cation and neutral ground states of order 2.0 and 2.5, respectively. The instability of Ge–C triple bonded species is attributed to the energy required for electronic promotion in the metal in order to achieve a hybrid configuration suitable for the formation of such a bond.

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

2001

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Die Photolyse eines Diazogermylens liefert eine Germylen‐Carben‐Spezies, eine Resonanzstruktur eines Germins (siehe Schema). Belege dafür, dass die dreifach gebundene Form bei der Abfangreaktion mit Alkoholen auftritt, sind die Befunde, dass sich die Diazovorstufe nicht wie ein Germylen verhält und dass das Photolyseprodukt nicht mit Carbenfängern wie 2,3‐Dimethylbutadien reagiert. Damit handelt es sich um den ersten chemischen Hinweis auf ein Germin. Ar=2,6‐(iPr2NCH2)2C6H3; R=Me, tBu.

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Nachweis von HCSiF und HCSiCl als die ersten Moleküle mit formalen C≡Si-Bindungen

Abstract: Die Neutralisierung von [C,H,Si,X] .+‐Radikalkationen (X=F, Cl) liefert den ersten experimentellen Beleg für die Existenz der neutralen Siline HC≡SiF und HC≡SiCl, die nach Ab‐initio‐MO‐Rechnungen nichtlineare Strukturen aufweisen (siehe Bild).

Cited by 27 publications

References 37 publications

Substituent Effects on the Stability of Thallium and Phosphorus Triple Bonds: A Density Functional Study

Substituent Effects on the Stability of Thallium and Phosphorus Triple Bonds: A Density Functional Study

Combined Quantum Chemical and Mass Spectrometry Study of [Ge,C,H]+ and Its Neutral Counterpart

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

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