钯β-二酮酸酯蒸气热表面热分解机理研究

P. P. Semyannikov, V. Grankin, I. Igumenov, A. Bykov
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引用次数: 6

摘要

采用高温分子束源,用高温质谱法研究了钯(II) β-二酮酸配合物的热分解过程。确定了钯配合物在气相过程中的分解是由自由基机制进行的,并依赖于温度。为了进一步证明自由基粒子的存在,用自旋阱法对加合物进行了质谱鉴定。配合物的气相热稳定性顺序为:Pd(hfac) 2 > Pd(tfac) 2 > Pd(dpm) 2 > Pd(acac) 2。这个顺序与固态的热稳定性相反。Pd(aa) 2和Pd(hfa) 2配合物在氘中的热分解表明,氘的存在强烈地加速了分解过程。
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Mechanism of Thermal Decomposition of Palladium β-Diketonates Vapour on Hot surface
The processes of thermal decomposition of palladium(II) β-diketonate complexes were investigated by a high-temperature mass spectrometric method with the use of a high-temperature molecular beam source. It was established that decomposition of the palladium complexes in gas phase processes proceeds by a radical mechanism and depends on temperature. For an additional proof of the existence of the radical particles the spin trap method was applied with a mass spectrometric identification of adducts. The following order of thermal stability of the complexes in gas phase was established: Pd(hfac) 2 > Pd(tfac) 2 > Pd(dpm) 2 > Pd(acac) 2 . This order is reverse to the thermal stability in a solid state. The thermal decomposition of Pd(aa) 2 and Pd(hfa) 2 complexes in deuterium showed that the deuterium presence strongly accelerates the decomposition processes.
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