Investigation into the reactivity of M(η5-C5R5)(CO)2(alkane) (M = Mn or Re; R = H, Me or Ph; alkane = n-heptane or cyclopentane) and Re(η5-C5H5)(CO)2(Xe) in solution at cryogenic and room temperature
Investigation into the reactivity of M(η5-C5R5)(CO)2(alkane) (M = Mn or Re; R = H, Me or Ph; alkane = n-heptane or cyclopentane) and Re(η5-C5H5)(CO)2(Xe) in solution at cryogenic and room temperature
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DOI：
10.1039/b001987i
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发表时间：
2000-01-01
期刊：
影响因子：
--
通讯作者：
George, MW
中科院分区：
文献类型：
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作者：
Childs, GI;Colley, CS;George, MW
用红外光谱法在低温（仅Re）和室温（仅R=H）下对一系列M（eta（5）-C5 R5）（CO）（2）（C5 H10）（R=H，Me或Ph; M=Mn或Re）配合物进行了表征。这些配合物的衰变率已被测量和比较相应的正庚烷类似物。这些比较表明，有机金属环戊烷配合物的寿命明显长于相关的正庚烷配合物。的烷烃配合物与CO的反应，确定高于室温的活化参数，表明这些配合物的反应性是由熵，而不是熵的因素。对全甲基化和全苯基化的双烯基环戊烷配合物的衰减速率的测量表明，它们对CO的反应性比Re（eta（5）-C5 H5）（CO）（2）（C5 H10）更强。配合物Re（eta（5）-C5 H5）（CO）（2）（n-C7 H16）在低温下在液体氙中的特征在于，衰减速率研究表明，在相似温度下，它与Re（eta（5）-C5 H5）（CO）（2）（n-C7 H16）在庚烷中具有相似的寿命。
A series of M(eta(5)-C5R5)(CO)(2)(C5H10) complexes (R=H, Me or Ph; M=Mn or Re) have been characterised at low (Re only) and room temperature (R=H only) using infrared spectroscopy. The decay rates of these complexes have been measured and compared to those of the corresponding n-heptane analogues. These comparisons show that the organometallic cyclopentane complexes are significantly longer-lived than the related n-heptane complexes. The activation parameters for the reaction of the alkane complexes with CO, determined above room temperature, suggest that the reactivity of these complexes is governed by entropic rather than enthalpic factors. The decay rates measured for the permethylated and perphenylated cyclopentadienyl rhenium cyclopentane complexes show that these are more reactive towards CO than Re(eta(5)-C5H5)(CO)(2)(C5H10). The complex Re(eta(5)-C5H5)(CO)(2)(Xe) has been characterised in liquid xenon at low temperature, with decay rate studies showing this to have a similar lifetime to Re(eta(5)-C5H5)(CO)(2)(n-C7H16) in heptane at a similar temperature.