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Reaction of carbene‐stabilized disilicon (1) with the lithium‐based dithiolene radical (2.) affords the first dianionic silicon tris(dithiolene) complex (3). Notably, the formation of 3 represents the unprecedented utilization of carbene‐stabilized disilicon (1) as a silicon‐transfer agent. The nature of 3 was probed by multinuclear NMR spectroscopy, single‐crystal X‐ray diffraction, and DFT computations. [ABSTRACT FROM AUTHOR]

Abstract: Whereas low‐temperature (−78 °C) reaction of the lithium dithiolene radical 1. with boron bromide gives the dibromoboron dithiolene radical 2., the parallel reaction of 1. with (C6H11)2BCl (0 °C) affords the dicyclohexylboron dithiolene radical 3.. Radicals 2. and 3. were characterized by single‐crystal X‐ray diffraction, UV/Vis, and EPR spectroscopy. The nature of these radicals was also probed computationally. Under mild conditions, 3. undergoes unexpected thiourea‐mediated B−C bond activation to give zwitterion 4, which may be regarded as an anionic dithiolene‐modified carbene complex of the sulfenyl cation RS+ (R=cyclohexyl). [ABSTRACT FROM AUTHOR]

Molecular SiO2 and other simple silicon oxides have remained elusive despite the indispensable use of silicon dioxide materials in advanced electronic devices. Owing to the great reactivity of silicon-oxygen double bonds, as well as the low oxidation state of silicon atoms, the chemistry of simple silicon oxides is essentially unknown. We now report that the soluble disilicon compound, L:Si=Si:L (where L: = :C{N(2,6-iPr2C6H3)CH}2), can be directly oxidized by N2O and O2 to give the carbene-stabilized Si2O3 and Si2O4 moieties, respectively. The nature of the silicon oxide units in these compounds is probed by spectroscopic methods, complementary computations and single-crystal X-ray diffraction. [ABSTRACT FROM AUTHOR]

Tris(pentamethylphenyl)gallium, (Me5C6)3Ga, was prepared by reaction of pentamethylphenylmagnesium bromide with gallium(III) chloride in diethyl ether. The title compound, characterized by 1H and 13C NMR, elemental analyses, and single crystal X-ray diffraction, crystallizes in the P1¯ (No. 2) space group with a=9.003(9) A˚, b=10.713(1) A˚, c=16.066(2) A˚, α=107.63 (3)°, β=97.63 (3)°, γ=90.08(3)°, for Z=2. Refinement converged at R1=0.050, wR2=0.11. The pentamethylphenyl ligands are configured about the gallium center in a propeller fashion at angles of 67.3°, 62.3°, and 60.9°. [Copyright &y& Elsevier]