Steric Switching From Photochemical to Thermal N2 Splitting: A Computational Analysis of the Isomerization Reaction {(Cp*)(Am)Mo}2(μ-η1:η1-N2) → {(Cp*)(Am)Mo}2(μ-N)2.
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ABSTRACT: A μ-η1:η1-N2-bridged Mo dimer, {(η5-C5Me5)[N(Et)C(Ph)N(Et)]Mo}2(μ-N2), cleaves dinitrogen thermally resulting in a crystallographically characterized bis-μ-N-bridged dimer, {(η5-C5Me5)[N(Et)C(Ph)N(Et)]Mo}2(μ-N)2. A structurally related Mo dimer with a bulkier amidinate ligand, ([N(iPr)C(Me)N(iPr)]), is only capable of photochemical dinitrogen activation. These opposing reactivities were rationalized as steric switching between the thermally and photochemically active species. A computational analysis of the geometric and electronic structures of intermediates along the isomerization pathway from Mo2(μ-η1:η
SUBMITTER: Krewald V
PROVIDER: S-EPMC6535493 | biostudies-literature | 2019
REPOSITORIES: biostudies-literature
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