H2MBH2 and M(μ-H)2BH2 Molecules Isolated in Solid Argon: Inter-element M=B and M−H−B Bonds ( M = Ge, Sn)
H2MBH2 and M(μ-H)2BH2 Molecules Isolated in Solid Argon: Inter-element M=B and M−H−B Bonds ( M = Ge, Sn)
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固体氩中分离的 H2MBH2 和 M(μ-H)2BH2 分子：元素间 M=B 和 M–H–B 键（M = Ge、Sn）
DOI：
10.1021/acs.inorgchem.7b03109
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发表时间：
--
影响因子：
4.6
通讯作者：
Riedel Sebastian
中科院分区：
文献类型：
--
作者：
Zhao Jie;Beckers Helmut;Huang Tengfei;Wang Xuefeng;Riedel Sebastian
激光烧蚀的硼原子与GeH 4分子反应生成新型锗叉硼烷H2 GeBH 2，在λ = 405 nm的光照射下发生光化学重排生成四氢硼酸锗Ge（μ-H）2BH 2。作为比较，硼原子只与SnH 4反应生成四氢硼酸锡Sn（μ-H）2BH 2。红外矩阵隔离光谱与氘取代和国家的最先进的量子化学计算被用来确定这些物种在固体氩。通过量子化学计算预测了H_2GeBH_2的平面结构，其中B-Ge键为缺电子键，键级为1.5，具有部分重键特征。在M（μ-H）_2BH_2（M = Ge，Sn）的情况下，B-H σ-键上的电子被给予M的空轨道，形成两个3c-2 e B-H-M氢键。
Laser-ablated boron atoms react with GeH4molecules to form novel germylidene borane H2GeBH2, which undergoes a photochemical rearrangement to the germanium tetrahydroborate Ge(μ-H)2BH2upon irradiation with light of λ = 405 nm. For comparison, the boron atom reactions with SnH4only gave the tin tetrahydroborate Sn(μ-H)2BH2. Infrared matrix-isolation spectroscopy with deuterium substitution and the state-of-the-art quantum-chemical calculations are used to identify these species in solid argon. A planar structure of H2GeBH2with an electron-deficient B–Ge bond with a partial multiple bond character (bond order = 1.5) is predicted by quantum-chemical calculations. In the case of M(μ-H)2BH2(M = Ge, Sn) two 3c–2e B–H–M hydrogen bridged bonds are formed by donation of electrons from the B–H σ-bonds into emptyp-orbitals of M.