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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Parahydrogen derived illumination of pyridine based coordination products obtained from reactions involving rhodium phosphine complexes
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Parahydrogen derived illumination of pyridine based coordination products obtained from reactions involving rhodium phosphine complexes

机译：从涉及铑膦配合物的反应中获得的吡啶基配位产物的对位氢衍生照明

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摘要

The reactions of RhCl(PBz_3)_3 with H_2 and pyridine or 4-methylpyridine yield RhCl(H)_2(PBz_3)_2(py)and RhCl(H)_2(PBz_3)_2(4-Me-py),respectively.These species undergo hydride site exchange via the loss of the pyridyl donor and formation of RhCl(H)_2(PBz_3)_2 which contains equivalent hydride ligands;for the py system the activation free energy,DELTAG_(300),is 57.4 +-0.1 kJ mol~(-1)while for 4-Me-py the value is 59.6 +-0.3 kJ mol~(-1).These products only showed parahydrogen enhancement in the corresponding hydride resonances when a sacrificial substrate was added to promote hydrogen cyCling.When RhCl(PPh_3),was used as the precursor similar observations were made,while when RhCl(PCy_3)_2(C_2H_4)was examined,H_2 addition led to the formation of the binuClear complex(H)_2Rh(PCy_3)_2(mu-Cl)_2Rh(H)_2(PCy_3)_2 which was differentiated from RhCl(H)_2(PCy_3)_2 on the basis of the similarity in diffusion coefficient(5.5 x 10~(-9)m~2 s~(-1))to that of(H)_2Rh(PPh_3)_2(mu-Cl)_2Rh(PPh_3)_2(5.3 x 10~(-9)m~2 s~(-1)).The detection of RhCl(H)_2(PCy_3)_2(py)was facilitated when pyridine was added to a solution of RhCl(PCy_3)_2(C_2H_4)before the introduction of H_2.During these reactions trace amounts of the double substitution products,RhCl(H)_2(phosphine)(py)_2,were also detected.
机译：RhCl（PBz_3）_3与H_2和吡啶或4-甲基吡啶的反应分别产生RhCl（H）_2（PBz_3）_2（py）和RhCl（H）_2（PBz_3）_2（4-Me-py）。物种通过吡啶基供体的丢失和形成含等价氢化物配体的RhCl（H）_2（PBz_3）_2进行氢化物位点交换;对于py系统，活化自由能DELTAG_（300）为57.4 + -0.1 kJ mol〜（-1）而4-Me-py的值为59.6 + -0.3 kJ mol〜（-1）。当添加牺牲底物以促进氢循环时，这些产物仅在相应的氢化物共振中显示出对氢增强。当使用RhCl（PPh_3）作为前体时，进行了相似的观察，而当检查RhCl（PCy_3）_2（C_2H_4）时，H_2的添加导致形成了binuClear配合物（H）_2Rh（PCy_3）_2（mu- Cl）_2Rh（H）_2（PCy_3）_2与RhCl（H）_2（PCy_3）_2的区别是基于扩散系数（5.5 x 10〜（-9）m〜2 s〜（-1） ））到（H）_2Rh（PPh_3）_2（mu-Cl）_2Rh（PPh_3）_2（5.3 x 1 0〜（-9）m〜2 s〜（-1））。将吡啶添加到RhCl（PCy_3）_2（C_2H_4）溶液中有助于RhCl（H）_2（PCy_3）_2（py）的检测。在这些反应中，还检测到痕量的双取代产物RhCl（H）_2（膦）（py）_2。

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