Sonochemistry of dimanganese decacarbonyl (Mn2(CO)10) and dirhenium decacarbonyl (Re2(CO)10)
Sonochemistry of dimanganese decacarbonyl (Mn2(CO)10) and dirhenium decacarbonyl (Re2(CO)10)
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十羰基二锰 (Mn2(CO)10) 和十羰基二铼 (Re2(CO)10) 的声化学
DOI：
10.1021/ja00357a014
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发表时间：
2002
期刊：
影响因子：
--
通讯作者：
P. Schubert
中科院分区：
文献类型：
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作者：
K. Suslick;P. Schubert
用高强度超声辐照液体，通过空化作用产生局部热点，其瞬时压力> 300 atm，温度约3000 K。我们报告了超声对Mn 2（CO）10，MnRe（CO）10和Re 2（CO）10的化学效应的第一次研究。超声波照射Mn 2（CO）10产生膦或亚磷酸酯的配体取代。这种取代的速率与配体的选择或其浓度无关，并且取代的机制不涉及金属-金属键断裂。MnRe（CO）10和Re 2（CO）10不会以明显的速率进行声化学配体取代，可能是因为它们的较低蒸气压排除了它们在空化事件中的存在。此外，我们已经发现，Mn 2（CO）10和Re 2（CO）10进行快速的声化学卤化与卤化碳溶剂，与105的速率增强。在这些卤化中的主要声化学事件是溶剂的均裂，产生卤素原子（其可以被M2（CO）10或烷烃溶剂捕获）和碳自由基（其二聚化并已被如此表征）。
Irradiationof liquids with high-intensity ultrasound creates, via cavitation, localized hot spots with transient pressures of> 300 atm and temperatures~ 3000 K. We report the first studies of the chemical effects of ultrasound on Mn2 (CO) 10, MnRe (CO) 10, and Re2 (CO) 10. Ultrasonic irradiation of Mn2 (CO) 10 produces ligand substitution by phosphines or phosphites. The rate of this substitution is independent of the choice of ligand or of its concentration, and the mechanism of substitution does not involve metal-metal bond cleavages. MnRe (CO) 10 and Re2 (CO) 10 do not undergo sonochemical ligand substitution at appreciable rates, presumably because their lower vapor pressures preclude their presence in the cavitation event. In addition, we have found that Mn2 (CO) 10 and Re2 (CO) 10 undergo rapid sonochemical halogenation with halocarbon solvents, with rate enhancement of 105. The primary sonochemial event in these halogenations is homolysis of the solvent, generating halogen atoms (which can be trapped by M2 (CO) 10 or by alkane solvent) and carbon radicals (which dimerize and have been so characterized).