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This article is protected by copyright. All rights reserved.We will argue that isolated, long-lived electronic states of ReC+serve as root cause for the distinctly different reactivities of this diatomic ion in the thermal activation of dihydrogen. Detailed high-level quantum chemical calculations support the experimental findings obtained in the highly diluted gas phase using FT-ICR mass spectrometry. The origin for the existence of these long-lived excited electronic states as well as their consequences for the varying mechanisms of di
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