部分氘化过渡金属三氢化物配合物中意想不到的同位素对交换耦合常数的影响

Ricard Gelabert, Miquel Moreno, José M. Lluch
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引用次数: 1

摘要

在本文中,我们试图解释当一个等效质子变成氘核时,配合物[CpIrL(H)3]+ (L=各种膦和亚磷酸盐配体)中氢化物的1H-NMR标量H-H偶联所显示的不寻常的同位素效应(D.M. Heinekey, J.M. Millar, T.F. Koetzle, N.G. Payne, K.W. Zilm, J. Am)。化学。社会科学。112,909(1990)]。我们发现,在比例物质的情况下,系统可以描述为一个三耦合阱系统,但当引入氘时,系统可以更好地描述为一个双耦合阱系统。最后,证明了双井系统的耦合大于等效三井系统的耦合,从而对所报道的实验事实给出了合理的解释。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
On the unexpected isotope effect on the exchange coupling constant in partially deuterated transition-metal trihydride complexes

In this paper we attempt to explain the unusual isotope effect displayed by the 1H-NMR scalar H-H coupling of the hydrides in complexes [CpIrL(H)3]+ (L=various phosphine and phosphite ligands) when one of the equivalent protons is turned into a deuteron (D.M. Heinekey, J.M. Millar, T.F. Koetzle, N.G. Payne, and K.W. Zilm, J. Am. Chem. Soc. 112, 909 (1990)]. It is found that in the case of the perprotio species the system can be described as a three-coupled well system, but when a deuterium is introduced the system is better described as a double-coupled well. Finally, it is shown that the coupling in the case of a double-well system is greater than in an equivalent triple-well system, in this way giving a plausible explanation to the experimental facts reported.

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