Titanium Cluster Nuclearity Controls the Potential of Ti(IV/III) Reduction by Transfer Hydrogenation

Titanium-containing clusters can be photoreduced in the presence of a hydrogen donor to form catalytically active Ti(III) centers. The cluster nuclearity is hypothesized to impact the thermodynamics of this process. To probe this, we examine a series of titanium polyoxometalates ranging from 3 to 17...

وصف كامل

محفوظ في:
التفاصيل البيبلوغرافية
المؤلف الرئيسي: Brian G. Diamond (21393975) (author)
مؤلفون آخرون: Robin E. Bumbaugh (21393978) (author), Christopher H. Hendon (1308372) (author)
منشور في: 2025
الموضوعات:
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الوصف
الملخص:Titanium-containing clusters can be photoreduced in the presence of a hydrogen donor to form catalytically active Ti(III) centers. The cluster nuclearity is hypothesized to impact the thermodynamics of this process. To probe this, we examine a series of titanium polyoxometalates ranging from 3 to 17 Ti-centers. Through an examination of both compositional and structural aspects of the clusters, we compare the favorability of proton-coupled electron transfer to and from the titanium clusters. The singly reduced cluster tends to have a consistent potential (approximately −5 eV vs vacuum) regardless of structure and nuclearity. Using a principal component analysis, we show that we can predict the energy of hydrogenation of the cluster and that it depends on both cluster nuclearity and composition and provides a clear pathway for Ti-based catalyst development.