Electrospray ionization‐mass spectrometry (ESI‐MS) of mixtures of AgBF₄ or AgNO₃ with the capping ligand bis(diphenylarsino)methane ((Ph₂As)₂CH₂ = dpam) in a solution of acetonitrile revealed the formation of the following cations: [Ag(CH₃CN)(dpam)]⁺, [Ag(dpam)₂]⁺, [Ag₂(Cl)(dpam)₂]⁺, and [Ag₃(Cl)₂(dpam)₃]⁺. Addition of NaBH₄ to these solutions results in the formation of the cluster cations [Ag₂(BH₄)(dpam)₂]⁺, [Ag₂(BH₄)(dpam)₃]⁺, [Ag₃(H)(BH₄)(dpam)₃]⁺, [Ag₃(BH₄)₂(dpam)₃]⁺, [Ag₃(H)(Cl)(dpam)₃]⁺, and [Ag₃(I)(BH₄)(dpam)₃]⁺, as established by ESI‐MS. Use of NaBD₄ confirmed that borohydride is the source of the hydride in these clusters. An Orbitrap Fusion LUMOS mass spectrometer was used to explore the gas‐phase unimolecular chemistry of selected clusters via multistage mass spectrometry (MSⁿ) experiments employing low‐energy collision‐induced dissociation (CID) and high‐energy collision‐induced dissociation (HCD) experiments. The borohydride containing clusters fragment via two competing pathways: (i) ligand loss and (ii) B–H bond activation involving BH₃ loss. Density functional theory (DFT) calculations were used to calculate the energetics of the optimized structures for all precursor ions, fragment ions, and neutrals and to estimate the reaction endothermicities. Generally, there is reasonable agreement between the most abundant product ion formed and the predicted endothermicity of the associated reaction channel. The DFT calculations predicted that the novel dimer [Ag₂(BH₄)(dpam)₂]⁺ has a paddlewheel structure in which the dpam and BH₄⁻ ligands bridge both silver centers.

中文翻译：

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使用电喷雾电离串联质谱研究在双（二苯基ar基）甲烷存在下，银盐与NaBH4反应生成的银纳米团簇的形成和气相化学

在乙腈溶液中的AgBF ₄或AgNO ₃与封端配体双（二苯基ar基）甲烷（（Ph ₂ As）₂ CH ₂ = dpam）的混合物的电喷雾电离质谱（ESI-MS）表明形成了以下物质阳离子：[Ag（CH ₃ CN）（dpam）] ⁺，[Ag（dpam）₂ ] ⁺，[Ag ₂（Cl）（dpam）₂ ] ⁺和[Ag ₃（Cl）₂（dpam）₃ ] ⁺。向这些溶液中添加NaBH ₄会导致形成簇阳离子[Ag₂（BH ₄）（dpam）₂ ] ⁺，[Ag ₂（BH ₄）（dpam）₃ ] ⁺，[Ag ₃（H）（BH ₄）（dpam）₃ ] ⁺，[Ag ₃（BH ₄）₂（dpam）₃ ] ⁺，[Ag ₃（H）（Cl）（dpam）₃ ] ⁺和[Ag ₃（I）（BH ₄）（dpam）₃ ] ⁺，由ESI‐MS确定。使用NaBD ₄证实硼氢化物是这些簇中氢化物的来源。使用Orbitrap Fusion LUMOS质谱仪通过采用低能碰撞诱导解离（CID）和高能碰撞诱导解离（HCD）的多级质谱（MS ⁿ）实验探索选定簇的气相单分子化学实验。含硼氢化物的团簇通过两个竞争途径断裂：（i）配体损失和（ii）涉及BH _3的B–H键活化失利。密度泛函理论（DFT）计算用于计算所有前体离子，碎片离子和中性离子的优化结构的能级，并估算反应的吸热性。通常，形成的最丰富的产物离子与相关反应通道的预计吸热度之间存在合理的一致性。在DFT计算预测，新颖二聚体将[Ag ₂（BH ₄）（DPAM）₂ ] ⁺具有水轮结构，其中DPAM和BH ₄ ^-配体桥接两个银中心。