Cyclobutenylidene: A Multifaceted Two-Coordinate Carbon Species Obtained via Skeletal Editing of a Cyclopropenylidene.

C4H4 isomers not only serve as a basis to understand the chemical properties of hydrocarbons but are possible intermediates in combustion and organic reactions in outer space. Cyclobutenylidene (CBY), an elusive C4H4 isomer, is often proposed as a key intermediate in transition-metal-catalyzed metathesis and cycloaddition reactions between carbon-carbon multiple bonds. The geometrical structure of cyclobutenylidene predicted by calculations had been debated as whether it should be regarded as a carbocyclic carbene or a strained bridgehead alkene. Here, we report the synthesis of a crystalline cyclobutenylidene derivative, namely, a 3-silacyclobut-2-en-4-ylidene (SiCBY) via "carbene-to-carbene ring-expansion" reaction of an isolable diaminocyclopropenylidene induced by a silicon analogue of a carbene (silylene). The SiCBY exhibits multifaceted electronic properties which are corroborated by its extremely strong electron-donating properties and ambiphilic reactivity toward small gaseous molecules and C-H bonds. This result introduces an exciting strategy as well as a molecular motif to access low-valent carbon species with unusual electronic properties.

Twisted push-pull disilenes obtained by direct 1,2-hydro/chloroborylation of a silylone.

Overcrowded 1-amino-2-boryldisilenes were isolated as blue crystals by the direct hydro/chloroborylation of a cyclic (alkyl)(amino)silylene-coordinated monatomic silicon complex (silylone) with 9-BBN (BBN = borabicyclo[3.3.1]nonane) hydride/chloride. The extreme twisting and push-pull effect around the SiSi bonds resulted in strong polarization of the SiSi bond. The disilenes exhibit longest-wavelength absorptions above 600 nm due to the charge-transfer-type π → π* transitions and undergo reversible 1,3-hydride/halide migration in solution reflecting the electrophilic terminal silicon atoms.

Synthesis, Structure and Electronic Properties of a Stable π-Type 3-Electron-2-Center-Bonded Species: A Silicon Analogue of a Bicyclo[1.1.0]butane Radical Anion.

σ-Type 3-electron-2-center (3e-2c) bonds have been extensively studied as one of the key bonding motifs in radical chemistry and some biological systems. "π-Type 3e-2c-bonded species" that contain a 3e-2c π-bond without an underlying σ-bond framework, however, have been unexplored so far both theoretically and experimentally. Herein, we report the synthesis of the first stable π-type 3e-2c-bonded species, a silicon analogue of a bicyclo[1.1.0]butane radical anion. This compound exhibits an extremely long bridgehead Si-Si bond (3.0638(8) Å) and a strong near-IR absorption at 922 nm in solution which arises from a HOMO→SOMO [π(Si-Si)→π*(Si-Si)] transition. DFT calculations revealed a π-type bonding interaction between the two bridgehead silicon atoms with an unpaired electron mainly delocalized across the corresponding π*-type orbital, which introduces a novel bonding motif for constructing π-electron systems.

Conformationally Switchable Silylone: Electron Redistribution Accompanied by Ligand Reorientation around a Monatomic Silicon.

Complexes that could be switched between two electronic states by external stimuli have attracted much attention for their potential application in molecular devices. However, a realization of such a phenomenon with low-valent main-group element-centered complexes remains challenging. Herein, we report the synthesis of cyclic (alkyl)(amino)silylene (CAASi)-ligated monatomic silicon(0) complexes (silylones). The bis(CAASi)-ligated silylone adopts a π-localized ylidene structure (greenish-black color) in the solid state and a π-delocalized ylidene structure (dark-purple color) in solution that could be reversibly switched upon phase transfer (ylidene [L: → :Si = L ↔ L = Si: ← :L]). The observed remarkable difference in the physical properties of the two isomers is attributed to the balanced steric demand and redox noninnocent character of the CAASi ligand which are altered by the orientation of the two terminal ligands with respect to the Si-Si-Si plane: twisted structure (π-localized ylidene) and planar structure (π-delocalized ylidene). Conversely, the CAASi/CDASi-ligated heteroleptic silylone (CDASi = cyclic dialkylsilylene) only exhibited the twisted π-localized ylidene structure regardless of the phase. The synthesized silylones also proved themselves as monatomic silicon surrogates. Thermolysis of the silylones in the presence of an ethane-1,2-diimine afforded the corresponding diaminosilylenes. Analyses of the products suggested a stepwise mechanism that proceeds via a disilavinylidene intermediate.

Intermolecular C-H Activation at the Allylic/Benzylic and Homoallylic/Homobenzylic Positions of Cyclic Hydrocarbons by a Stable Divalent Silicon Species.

Direct activation of inert C(sp3 )-H bonds by main group element species is yet a formidable challenge. Herein, the dehydrogenation of cyclohexene and 1,2,3,4-tetrahydronaphthalene through the allylic/benzylic and homoallylic/homobenzylic C-H bond activation by cyclic (alkyl)(amino)silylene 1 in neat conditions is reported to yield the corresponding aromatic compounds. As for the reaction of cyclohexene, allylsilane 3 and 7-silanorbornene 4 were also observed, which could be interpreted as a direct dehydrogenative silylation reaction of monoalkenes at the allylic positions. Experimental and computational studies suggest that the dehydrogenation of cyclohexene at the homoallylic position was accomplished by a combination of silylene 1 and radical intermediates such as hydrosilyl radical INT1 or cyclohexenyl radical H, which are generated in the initial step of the reaction.

1,4-Dehydrogenation with a Two-Coordinate Cyclic (Alkyl)(amino)silylene.

Cyclic (alkyl)(amino)silylene (CAASi) 1 has been found to successfully dehydrogenate 1,4-dihydroaromatic compounds containing various substituents to afford the corresponding aromatic compounds. The observed high substrate generality proves 1 to be a potential 1,4-dehydrogenation reagent for organic compounds. For the reaction with 9,10-dimethyl-9,10-dihydroanthracene, silylene 1 activated not only benzylic C-H bonds but also aromatic C-H bonds to yield a silaacenaphthene derivative, which is an unprecedented reaction of silylenes. The results of the experimental and computational study of the reaction of CAASi 1 with 9,10-dihydroanthracene and 1,4-cyclohexadiene are consistent with the notion that 1,4-dehydrogenation with CAASi 1 proceeds mainly through a stepwise hydrogen-abstraction mechanism.