Stannaacetylene (RSn⋮CR‘) Showing Carbene-like Reaction Mode

Setaka, Wataru; Hirai, Katsuyuki; Tomioka, Hideo; Sakamoto, Kenkichi; Kira, Mitsuo

doi:10.1021/ja0389974

Cited by 44 publications

(45 citation statements)

References 22 publications

(8 reference statements)

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“…ular for germanium and tin: for these elements stable dicoordinated compounds REX (with X groups susceptible to substitution, for example in salt metathesis reactions) have been known for several years. Consequently, in 2001 the Couret group [8] and three years later Sakamoto, Kira, and coworkers [9] provided evidence for short-lived germynes and stannynes that form during photolysis of the corresponding methyldiazo compounds (Scheme 2). In both cases only trapping products, either from intermolecular (E = Ge) or intramolecular follow-up reactions (E = Sn) were isolated.…”

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“…Photolysis experiments at 77 K in a methylpentane matrix indicated that the stannyne persists under these conditions and laser flash photolysis experiments suggested a lifetime of approximately 50 ms at room temperature. [9] In the case of silicon the synthesis of the intramolecular phosphanyl-stabilized chlorosilylene 7 paved the way for the preparation of silyne 6 (Scheme 3). [5] Further functionalization of silylene 7 to give diazomethylsilylene 8 and its photolysis at À60 8C gave the dark red silyne 6 in 68 % yield.…”

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A Compound with a Si–C Triple Bond

Lühmann¹,

Müller²

2010

Angew Chem Int Ed

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carbenes · main-group elements · multiple bonds · organosilicon compoundsDespite the impressive progress made in the last decade in the chemistry of multiple-bonded main-group compounds, triple bonds between carbon and its heavier homologues still have the touch of unattainability.[1] Efforts to synthesize stable or even only persistent compounds that feature an E À C triple bond (E = Si, Ge, Sn, Pb) face several principal obstacles. On the one hand, there is the essential reluctance of the heavier elements to engage in multiple bonds. As a result only relatively weak p bonds with small HOMO/ LUMO energy differences are formed and consequently these compounds show extreme reactivity towards addition reactions and nucleophilic and electrophilic attack. This problem has been solved for compounds containing homonuclear EE bonds by using extremely bulky substituents. In addition, heteroleptic EE' bonds are always polarized owing to the different electronegativity of the constituent atoms. Because of the relative high electronegativity of carbon, the polarization of the triple bond is extreme for carbynes, RE CR'. This further increases the reactivity of these compounds and severely complicates their synthesis and isolation.All recent high-level calculations of the [CSiH 2 ] potential energy surface predict that the classical linear silyne 1, the analogue of acetylene, is not at an energy minimum, but that a second-order Jahn-Teller distortion forces it into a trans bent structure 2.[2] This parallels the situation found for disilynes, RSiSiR. The results of the calculations, however, reveal a second important aspect: Silyne 2 is thermodynamically and kinetically unstable, and undergoes unimolecular isomerization to silavinylidene 3. Specifically, trans bent silyne 2 is less stable than monocoordinated silylene 3 by 143 kJ mol À1 and the barrier for the 1,2-H shift which converts 2 into 3, is rather small, merely 21 kJ mol À1

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A Compound with a Si–C Triple Bond

Lühmann¹,

Müller²

2010

Angew Chem Int Ed

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“…By photolyzing REC(N 2 )R′ to denitrogenation following by capture reactions of the formed intermediate, Bibal et al. [7] and Setaka et al [8] have indirectly shown the existence of the triply bonded RE≡≡CR′(E=Ge, Sn). However, for Pb≡≡C triply bonding, to the best of our knowledge, we are not aware of any theoretical and experimental reports.…”

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PbCNN: A molecule containing Pb≡C bonding

Zhang

Shi

et al. 2009

Sci. China Ser. B-Chem.

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In order to predict potential molecules with Pb≡≡C bonding, we investigated the potential energy surface of a tetra-atomic system [PbCN 2 ] at the CCSD(T)//B3LYP level. We found that the linear isomer PbCNN possesses good thermodynamic and kinetic stability. The combined molecular orbital analysis, hydrogenation heat, bond energy and bond dissociation energy all proved that PbCNN is composed of Pb≡≡ C triple bonding.PbCNN, triple bonding, potential energy surface

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“…B. bei Salzmetathesen sind) zugänglich. Konsequenterweise konnten 2001 die Gruppe um Couret [8] und drei Jahre später Sakamoto, Kira et al [9] Hinweise auf kurzlebige Germine und Stannine während Photolysereaktionen der entsprechenden Methyldiazoverbindungen vorlegen (Schema 2). In beiden Fällen wurden nur Abfangprodukte durch intermolekulare (E = Ge) oder intramolekulare Folgereaktionen (E = Sn) isoliert.…”

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“…50 ms bei Raumtemperatur schließen. [9] Im Falle des Siliciums bereitete die Synthese des intramolekular phosphanylstabilisierten Chlorsilylens 7 den Weg für die Synthese des Silins 6 (Schema 3). [5] Eine weitere Funktionalisierung des Silylens 7 zum Diazomethylsilylen 8 und dessen anschließende Photolyse bei À60 8C ergaben das dunkelrote Silin 6 in 68 % Ausbeute.…”

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