首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >A Gas-Phase Study of the Kinetics of Formation of Fe(CO)_3DMB,Fe(CO)_3(DMB)_2,and Fe(CO)_4DMB:The Bond Dissociation Enthalpy for Fe(CO)_3(DMB)_2 (DMB=3,3-dimethyl-1-butene)
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A Gas-Phase Study of the Kinetics of Formation of Fe(CO)_3DMB,Fe(CO)_3(DMB)_2,and Fe(CO)_4DMB:The Bond Dissociation Enthalpy for Fe(CO)_3(DMB)_2 (DMB=3,3-dimethyl-1-butene)

机译:Fe(CO)_3DMB,Fe(CO)_3(DMB)_2和Fe(CO)_4DMB形成动力学的气相研究:Fe(CO)_3(DMB)_2(DMB)的键解离焓= 3,3-二甲基-1-丁烯)

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摘要

The transient spectra of Fe(CO)_3(3,3-dimethyl-1-butene) and Fe(CO)_3(3,3-dimethyl-1-butene)_2 have been obtained in the carbonyl stretching region of the infrared.Fe(CO)_4(3,3-dimethyl-1-butene)has also been monitored.The bond dissociation enthalpy for loss of 3,3-dimethyl-1-butene (DMB) from Fe(CO)_3(DMB)_2 has been determined as 15.2+-3.8 kcal mol~(-1).The rate constants for the reactions of Fe(CO)_3+DMB,Fe(CO)_3DMB+DMB,Fe(CO)_4+DMB,and Fe(CO)-3DMB+CO have been measured as (9.6+-1.4)X10~(-11),(2.3+-0.8)X10~(-12),(5.0+_0.5)X10~(-13),and (3.9+-0.6)X10~(-12) cm~3 molecule~(-1) s~(-1),respectively.The effects of the polarizability and steric interaction energy of the ligand on the bimolecular rate constants for the reactions of Fe(CO)_3 L+L(L=olefin)complexes are discussed.A correlation between these rate constants and the steric interaction energy divided by the magnitude of the polarizability of the ligand is observed.An estimate for the rate constant for addition of 1-pentene to Fe(CO)_3(1-pentene),based on data and correlations from this study,does not lead to a significant change in calculated thermodynamic parameters for ptocesses relevant to the isomerization of pentene.Factors that could influence the stability of Fe(CO)_3 L_2 complexes are also discussed.
机译:Fe(CO)_3(3,3-二甲基-1-丁烯)和Fe(CO)_3(3,3-二甲基-1-丁烯)_2的瞬态光谱已在红外的羰基拉伸区域获得。还监测了Fe(CO)_4(3,3-二甲基-1-丁烯).Fe(CO)_3(DMB)_2失去3,3-二甲基-1-丁烯(DMB)的键解离焓Fe(CO)_3 + DMB,Fe(CO)_3DMB + DMB,Fe(CO)_4 + DMB,Fe(CO)_3 + DMB,Fe(CO)_3DMB + DMB,Fe(CO)_4 + DMB和Fe( CO)-3DMB + CO的测量值为(9.6 + -1.4)X10〜(-11),(2.3 + -0.8)X10〜(-12),(5.0 + _0.5)X10〜(-13),和(3.9 + -0.6)X10〜(-12)cm〜3分子〜(-1)s〜(-1)。配体的极化率和空间相互作用能对双分子速率常数的影响讨论了Fe(CO)_3 L + L(L =烯烃)络合物的反应,观察到这些速率常数与空间相互作用能除以配体极化率的相关性。 1-戊烯加到Fe(C O)_3(1-戊烯),基于本研究的数据和相关数据,不会导致与戊烯异构化有关的工艺的热力学参数的显着变化。影响Fe(CO)_3稳定性的因素还讨论了L_2配合物。

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