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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis, structure, and condensed-phase reactivity of [Ag-3(mu(3)-H)(mu(3)-BH4)L-3(Ph)](BF4) (L-Ph = bis(diphenylphosphino) amine) with CS2
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Synthesis, structure, and condensed-phase reactivity of [Ag-3(mu(3)-H)(mu(3)-BH4)L-3(Ph)](BF4) (L-Ph = bis(diphenylphosphino) amine) with CS2

机译：[Ag-3（3）-H）（mu（3）-b4）L-3（pH）]（bf4）（L-pH =双（二苯基膦基）胺（L-pH =双（二苯基膦基）胺的合成，结构和浓缩相反应性 ）与cs2.

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Electrospray ionisation mass spectrometry (ESI-MS) was used to monitor the reaction of AgBF4, bis(diphenylphosphino) amine (dppa = (Ph2P)(2)NH = L-Ph) and NaBH4 in acetonitrile and thereby direct the synthesis of the silver nanocluster [Ag-3(mu(3)-H)(mu(3)-BH4)L-3(Ph)](BF4), 3b.BF4, formed via reaction of AgBF4, bis(diphenylphosphino) amine (dppa = (Ph2P)(2)NH = L-Ph) and NaBH4 in acetonitrile. The X-ray structure of 3b.BF4 highlights that the cation adopts a planar trinuclear Ag-3 geometry surrounded by three dppa ligands and coordinated on the bottom face by a mu(3)-hydride and on the top face by a mu(3)-BH4. The solution phase structure of 3b.BF4 was characterised by multinuclear NMR and DOSY NMR, which showed that the borohydride anion remains bound in the [Ag-3(mu(3)-H)(mu(3)-BH4) L-3(Ph)](+) cluster cation in solution. ESI-MS and in situ H-1 and HSQC NMR spectroscopy reveals that 3b.BF4 reacts with CS2 in solution at the BH4 site to yield [Ag-3(H)(S2CH)L-3(Ph)](+), 4b, which has to date eluded structural characterisation via X-ray crystallography due to lack of formation of suitable crystals. The gas-phase ion chemistry of [Ag-3(H)(S2CH)L-3(Ph)](+) was examined under multistage mass spectrometry conditions using collision-induced dissociation (CID) and compared to that of the previously examined copper analogue, [Cu-3(H)(S2CH)L-3(Ph)](+). While both cluster cations fragment via ligand loss, the CID spectra of the resultant [M3(H)(S2CH) LPh 2]+ are different. Unlike [Cu-3(H)(S2CH) L-2(Ph)](+), which solely undergoes loss of thioformaldehyde to give [Cu-3(S)L-2(Ph)](+), [Ag-3(H)(S2CH)L-2(Ph)](+) gives a richer CID spectrum with fragmentation channels that include ligand loss, CH2S loss and reductive elimination of dithioformic acid. DFT calculations exploring rearrangement and fragmentation of the model systems [M-3(H)(S2CH)L-2(Me)]+ ((Me2P)(2)NH = dmpa = L-Me) were used to suggest plausible mechanisms and examine the energetics of the three competing channels:
机译：电喷雾电离质谱（ESI-MS）用于监测AgBF4，双（二苯基膦基）胺（DPPA =（Ph2P）（2）NH = L-PH）和NaBH 4的在乙腈中反应，从而引导所述银的合成纳米团簇将[Ag-3（亩（3）-H）（亩（3）-BH4）L-3（PH）]（BF 4），3b.BF4，经由AgBF4反应形成，双（二苯基膦基）胺（DPPA = （Ph2P）（2）NH = L-PH）和NaBH 4在乙腈。该阳离子采用平面三核的Ag-3几何3b.BF4亮点的透视结构围绕由三个DPPA配体和由协调亩在底面（3）和-hydride在由亩的顶面（3 ）-BH4。 3b.BF4的溶液相结构的特点是多核NMR和DOSY NMR测定，其结果表明，硼氢化物阴离子保持在将[Ag-3结合的（亩（3）-H）（亩（3）-BH4）L-3 （PH）]（+）簇阳离子在溶液中。 ESI-MS和原位H-1和HSQC NMR谱表明，与CS2 3b.BF4发生反应在在BH4现场解决产量将[Ag-3（H）（S2CH）L-3（PH）]（+），如图4B所示，其具有迄今为止，由于缺乏合适的形成晶体的躲避通过X射线晶体结构表征。的气相离子化学将[Ag-3（H）（S2CH）L-3（PH）]（+）使用碰撞诱导解离（CID）的多级质谱条件下检查和相比于先前被检验的铜类似物，[铜 - 3（H）（S2CH）L-3（PH）]（+）。虽然这两个集群的阳离子通过配体损失片段，将所得的CID谱[M3（H）（S2CH）LPH 2] +是不同的。不像[铜 - 3（H）（S2CH）L-2（PH）]（+），其仅经历的硫甲醛损失，得到[铜-3（S）L-2（PH）]（+），将[Ag -3（H）（S2CH）L-2（PH）]（+）给出了碎裂通道，包括配位体损失，CH2S损失和dithioformic酸的还原消除了更丰富的CID谱。 DFT计算探索模型系统的重排和碎裂[M-3（H）（S2CH）L-2（ME）] +（（Me2P）（2）NH = DMPA = L-ME）被用于暗示似是而非的机制和检查三个竞争渠道的热力学：

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