The reaction of M(CO)_3(PH_2PCH_2CH_2PPH_2)(M = Fe,Ru)withparahydrogen:probing the electronic structure of reaction intermediates and the internal rearrangement mechanism for the dihydride products

Daniele Schott; Philip Callaghan; John Dunne

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The reaction of M(CO)_3(PH_2PCH_2CH_2PPH_2)(M = Fe,Ru)withparahydrogen:probing the electronic structure of reaction intermediates and the internal rearrangement mechanism for the dihydride products

机译：M（CO）_3（PH_2PCH_2CH_2PPH_2）（M = Fe，Ru）与对氢的反应：探讨反应中间体的电子结构和二氢产物的内部重排机理

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The photochemical reaction of Ru(CO)_3(dppe)and Fe(CO)_3(dppe)(dppe = PH_2PCH_2CH_2PPH_2)with parahydrogen has been studied by in situ-photochemistry resulting in NMR spectra of Ru(CO)_2(dppe)(H)_2 that show significant enhancement of the hydride resonances while normal signals are seen in Fe(CO)_2(dppe)(H)_2.This effect is associated with a singlet electronic state for the key intermediate Ru(CO)_2(dppe)while Fe(CO)_2(dppe)is a triplet.DFT calculations reveal electronic ground states consistent with this picture.The fluxionality of Ru(CO)_2(dppe)(H)_2 and Fe(CO)_2(dppe)(H)_2 has been examined by NMR spectroscopy and rationalised by theoretical methods which show that two pathways for ligand exchange exist.In the first,the phosphorus and carbonyl centres interchange positions while the two hydride ligands are unaffected.A second pathway involving interchange of all three ligand sets was found at slightly higher energy.The H-H distances in the transition states are consistent with metal-bonded dihydrogen ligands.However,no local minimum(intermediate)was found along the rearrangement pathways.

机译：通过原位光化学研究了Ru（CO）_3（dppe）和Fe（CO）_3（dppe）（dppe = PH_2PCH_2CH_2PPH_2）与对氢的光化学反应，得出Ru（CO）_2（dppe）（ H）_2表现出氢化物共振的显着增强，而在Fe（CO）_2（dppe）（H）_2中则可以看到正常信号。此效应与关键中间体Ru（CO）_2（dppe）的单重电子态相关Fe（CO）_2（dppe）是三重态.DFT计算揭示了与此图一致的电子基态.Ru（CO）_2（dppe）（H）_2和Fe（CO）_2（dppe）（ H）_2已通过NMR光谱进行了检查，并通过理论方法进行了合理化处理，结果表明存在两个交换配体的途径。第一个途径是磷和羰基中心互换位置，而两个氢化物配体不受影响。发现三个配体组的能量略高。过渡态的HH距离与金属一致键合的二氢配体。但是，在重排途径中未发现局部最低值（中间值）。

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《Dalton transactions: An international journal of inorganic chemistry》 |2004年第20期|共7页
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Daniele Schott; Philip Callaghan; John Dunne;
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1. The reaction of M(CO)_3(PH_2PCH_2CH_2PPH_2)(M = Fe,Ru)withparahydrogen:probing the electronic structure of reaction intermediates and the internal rearrangement mechanism for the dihydride products [J] . Daniele Schott, Philip Callaghan, John Dunne Dalton transactions: An international journal of inorganic chemistry . 2004,第20期

机译：M（CO）_3（PH_2PCH_2CH_2PPH_2）（M = Fe，Ru）与对氢的反应：探讨反应中间体的电子结构和二氢产物的内部重排机理
2. Theoretical description of reaction mechanisms: reaction pathways and electronic structure rearrangements [J] . Peter B. Karadakov Annual Reports on the Progress of Chemistry, Section C. Physical Chemistry . 2001,第0期

机译：反应机理的理论描述：反应路径和电子结构重排
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机译：加标和开链簇氢化物与Au配合物的反应：杂金属簇[Au_2Ru_4（CO）_（12）（＃mu＃_4-PCF_3）（PMe_3）_2]和[Au_2Ru_4（CO）_（ 12）（＃mu＃_3-PCF_3）_2（PPh_3）_2]
4. Peripheral Reaction Mechanisms in Intermediate Energy Heavy-Ion Reactions [C] . D.E.Russ, A.C.Mignerey, E.J.Garcia-Solis, Winter workshop on nuclear dynamics . 1998

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机译：中间能量的质子诱导反应的激发函数和产率导致重要的诊断放射性同位素（sup 52）Fe，（sup 77）Br，（sup 82）Rb，（sup 97）Ru，（sup 111）In，（sup 123） I，（sup 127）Xe，（sup 128）Cs，（sup 178）Ta和（sup 201）Tl

The reaction of M(CO)_3(PH_2PCH_2CH_2PPH_2)(M = Fe,Ru)withparahydrogen:probing the electronic structure of reaction intermediates and the internal rearrangement mechanism for the dihydride products

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