Synthesis, structure and gas-phase reactivity of the mixed silver hydride borohydride nanocluster [Ag3(μ3-H)(μ3-BH4)L(Ph)3]BF4 (L(Ph) = bis(diphenylphosphino)methane).
Synthesis, structure and gas-phase reactivity of the mixed silver hydride borohydride nanocluster [Ag3(μ3-H)(μ3-BH4)L(Ph)3]BF4 (L(Ph) = bis(diphenylphosphino)methane).
复制标题
DOI：
10.1039/c5nr05690j
复制
发表时间：
2015-10
期刊：
影响因子：
6.7
通讯作者：
Athanasios Zavras;Alireza Ariafard;George N. Khairallah;J. White;R. Mulder;A. Canty;R. O'hair
中科院分区：
文献类型：
--
作者：
Athanasios Zavras;Alireza Ariafard;George N. Khairallah;J. White;R. Mulder;A. Canty;R. O'hair
硼氢化物与银盐反应，得到跨越多个尺度的产物，从离散的单核化合物到银纳米颗粒和胶体。用电喷雾质谱法研究了硼氢化钠、银（I）四氟硼酸盐和双（二甲基膦基）甲烷（L（Me））或双（二苯基膦基）甲烷（L（Ph））溶液中的团簇阳离子[Ag 3（H）（BH 4）L 3]（+）。将NaBH 4加入到AgBF 4和L（Ph）的乙腈溶液中，冷却至约100 ℃。-10 °C时，我们已经能够分离出第一个混合的氢化物硼氢化银纳米团簇[Ag 3（μ3-H）（μ3-BH 4）L（Ph）3] BF 4，并通过X射线晶体学对其进行结构表征。结合气相实验（L（Me）和L（Ph））和DFT计算（L（Me））揭示了从阳离子络合物[Ag 3（H）（BH 4）L3]（+）中损失配体如何提供几何形状的变化，该变化促进随后的BH 3损失以产生二氢化物簇[Ag 3（H）2Ln]（+）（n = 1和2）。结合先前研究的结果（Girod等人，化学-欧洲药典J.，2014，20，16626），这提供了混合的氢化银/硼氢化物纳米团簇、氢化银纳米团簇和银纳米团簇之间的直接连接。
Borohydrides react with silver salts to give products that span multiple scales ranging from discrete mononuclear compounds through to silver nanoparticles and colloids. The cluster cations [Ag3(H)(BH4)L3](+) are observed upon electrospray ionization mass spectrometry of solutions containing sodium borohydride, silver(I) tetrafluoroborate and bis(dimethylphosphino)methane (L(Me)) or bis(diphenylphosphino)methane (L(Ph)). By adding NaBH4 to an acetonitrile solution of AgBF4 and L(Ph), cooled to ca. -10 °C, we have been able to isolate the first mixed silver hydride borohydride nanocluster, [Ag3(μ3-H)(μ3-BH4)L(Ph)3]BF4, and structurally characterise it via X-ray crystallography. Combined gas-phase experiments (L(Me) and L(Ph)) and DFT calculations (L(Me)) reveal how loss of a ligand from the cationic complexes [Ag3(H)(BH4)L3](+) provides a change in geometry that facilitates subsequent loss of BH3 to produce the dihydride clusters, [Ag3(H)2Ln](+) (n = 1 and 2). Together with the results of previous studies (Girod et al., Chem. - Eur. J., 2014, 20, 16626), this provides a direct link between mixed silver hydride/borohydride nanoclusters, silver hydride nanoclusters, and silver nanoclusters.