Synthesis and Characterization of Molybdenum N-Heterocyclic Phosphenium and Phosphido Complexes
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Date
2021-05
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The Ohio State University
Abstract
In this work, a variety of synthetic and computational studies unified by the theme of cooperativity in catalyst design are described. Although noble metals are used abundantly in the field of catalysis, they are not abundant in the Earth's crust. As such, the strategies of both metal-ligand cooperativity and metal-metal cooperativity offer sustainable alternatives by enabling desirable chemistry at base metals. In both cooperative strategies, the redox burden at a metal is alleviated by a ligand or additional metal that is capable of either chemical modification or direct substrate bond activation. In this work, coordination of a N-heterocyclic phosphine (NHP) pincer ligand to a molybdenum carbonyl fragment is explored. Evidence for both formally phosphenium (NHP+) and phosphido (NHP-) molybdenum carbonyl complexes synthesized from it are presented, highlighting the ligand's redox non-innocence. The phosphenium complex or a derivative thereof may be capable of σ bond activation, though reactivity is not explored in this work.
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Keywords
inorganic synthesis, n-heterocyclic phosphine, metal-ligand cooperativity, molybdenum carbonyl, redox non-innocent ligand