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首页> 外文期刊>Chemistry: A European journal >Generation,Characterization,and Electrochemical Behavior of the Palladium-Hydride Cluster [Pd3(dppm)3(mu_3-CO)(mu_3-H)]~+(dppm = Bis(diphenylphosphinomethane)
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Generation,Characterization,and Electrochemical Behavior of the Palladium-Hydride Cluster [Pd3(dppm)3(mu_3-CO)(mu_3-H)]~+(dppm = Bis(diphenylphosphinomethane)

机译：氢化钯簇[Pd3（dppm）3（mu_3-CO）（mu_3-H）]〜+（dppm =双（二苯基膦基甲烷）的生成，表征和电化学行为

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摘要

Addition of formate on the dicationic cluster [Pd3(dppm)3(mu_3-CO)]~(2+)(dppm = bis(diphenylphosphi-nomethane)affords quantitatively the hydride cluster [Pd3(dppm)3(mu_3-CO)(mu_3-H)]~+.This new palladium-hydride cluster has been characterised by ~1H NMR,~(31)P NMR and UV/Vis spectroscopy and MALDI-TOF mass spectrometry.The unambiguous identification of the capping hydride was made from ~2H NMR spectroscopy by using DCO_2~-as starting material.The mechanism of the hydride complex formation was investigated by UV/Vis stop-ped-flow methods.The kinetic data are consistent with a two-step process in- volving:1)host-guest interactions between HCO_2~-and [Pd3(dppm)3(mu_3-CO)]~(2+)and 2)a reductive elimination of CO2.Two alternatives routes to the hydride complex were also examined:1)hydride transfer from NaBH4 to [Pd3(dppm)3(mu_3-CO)]~(2+)and 2)electrochemical reduction of [Pd3(dppm)3(mu_3-CO)]~(2+)to [Pd3(dppm)3(mu_3-CO)]~0 followed by an addition of one equivalent of H~+.Based on cyclic voltammetry,evidence for a dual mechanism(ECE and EEC;E = electrochemical(one-electron transfer),C = chemical(hydride dissociation))for the two-electron reduction of [Pd3(dppm)3(mu_3-CO)-(mu_3-H)]+ to [Pd3(dppm)3(mu_3-CO)]~0 is provided,corroborated by digital simulation of the experimental results.Geometry optimisations of the [Pd3(H2PCH2PH2)3(mu_3-CO)(mu_3-H)r model clusters were performed by using DFT at the B3LYP level.Upon one-electron reductions,the Pd-Pd distance increases from a formal single bond(n = + 1),to partially bonding(n = 0),to weak metal-metal interactions(n = - 1),while the Pd-H bond length remains relatively the same.
机译：在甲酸簇[Pd3（dppm）3（mu_3-CO）]〜（2 +）（dppm =双（二苯基膦基无甲烷））上添加甲酸盐定量地氢化物簇[Pd3（dppm）3（mu_3-CO）（ mu_3-H）]〜+。这种新的氢化钯簇通过〜1H NMR，〜（31）P NMR，UV / Vis光谱和MALDI-TOF质谱进行了表征。以DCO_2〜-为原料进行〜2H NMR光谱分析。通过UV / Vis停止流动方法研究了氢化物配合物的形成机理。动力学数据与两步法一致，包括：1） HCO_2〜-和[Pd3（dppm）3（mu_3-CO）]〜（2+）之间的主客体相互作用以及2）还原性消除CO2。还研究了氢化物配合物的两种替代途径：1）氢化物转移从NaBH4到[Pd3（dppm）3（mu_3-CO）]〜（2+）和2）[Pd3（dppm）3（mu_3-CO）]〜（2+）的电化学还原成[Pd3（dppm）3 （mu_3-CO）]〜0，然后加一当量的H〜+。基于循环体积测速法，[Pd3（dppm）3（mu_3-CO）-（Pd3（dppm）3）的双电子还原的双重机理的证据（ECE和EEC; E =电化学（单电子转移），C =化学（氢化物离解）） mu_3-H）] +到[Pd3（dppm）3（mu_3-CO）]〜0，通过实验结果的数字模拟得到证实。[Pd3（H2PCH2PH2）3（mu_3-CO）（mu_3）的几何优化-H）r模型簇是通过在B3LYP水平使用DFT进行的。在单电子还原时，Pd-Pd距离从形式单键（n = + 1）到部分键合（n = 0）到金属与金属之间的相互作用较弱（n =-1），而Pd-H键的长度则保持相对不变。

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