Reactivity of extremely bulky silylaminogermylene chloride and bonding analysis of a cubic tetragermylene
The low-valent germanium compounds with ultra-bulky silylamino groups can construct novel chemical structures and provide new discoveries with academic importance.The two-coordinated ultra-bulky silylamino germylene chloride Ge(N(SiPr3)2)Cl(1)has an empty 4p-orbital and a lone pair.Two reactions of thermal structural conversion and oxidation addition with phenanthrenequinone on the two activities of 1 were investigated.The ther-mal decomposition of 1 generated tetragermylene Ge4(NSiPr3)4(2)with cubic molecular structure,and its oxidative addition quantitatively with phenanthrenequinone(L)furnished aminomonochlorogermanium(Ⅳ)phenanthren-9,10-diolate:[Ge(N(SiPr3)2)(L)Cl](3).Their single-crystal structures and composition were fully characterized.Tetragermylene 2 is essentially a tetrameric adduct of isogermanitrile,its molecular structure exhibits a distorted cubic configuration,and four Ge atoms and four N atoms exist at the eight vertices of the central cubic skeleton.The Ge—N bond length is 0.2036(3)nm,the bond angles of N—Ge—N and Ge—N—Ge are 85.51(18)° and 94.32(16)°,respectively,and the side of the cubic skeleton is close to a planar parallelogram.Theoretical calcula-tion reveals for the first time the bonding of 2.The natural bond orbital(NBO)investigation provided a total of 20 molecular orbitals on the Ge4N4 skeleton.Additionally,the localized orbitals presented three energy levels of-12.22,-15.12,and-20.12 eV,for four Ge lone pairs,12 Ge—N bonds and four Si—N bonds,respectively.The Ge lone pair mainly remains the 4s character,while the Ge—N bond is contributed by the orbitals of 2s(18.4％)and 2p(71.3％)on N atom,4s(0.75％)and 4p(9.43％)on Ge atom.In the molecule of 3,the sp3 hybridized GeⅣ is coordi-nated by four donor atoms and exhibits a distorted tetrahedral configuration,because of the steric hindrance and asymmetric bonding.CCDC:2336001,2;2336000,3.
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