Controlled Expansion of a Strong‐Field Iron Nitride Cluster: Multi‐Site Ligand Substitution as a Strategy for Activating Interstitial Nitride Nucleophilicity |
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| Authors: | Myles J Drance Dr Charles C Mokhtarzadeh Dr Mohand Melaimi Dr Douglas W Agnew Dr Curtis E Moore Prof?Dr Arnold L Rheingold Prof?Dr Joshua S Figueroa |
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| Affiliation: | 1. Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, CA, USA;2. UCSD-CNRS Joint Research Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California, USA |
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| Abstract: | Multimetallic clusters have long been investigated as molecular surrogates for reactive sites on metal surfaces. In the case of the μ4‐nitrido cluster Fe4(μ4‐N)(CO)12]?, this analogy is limited owing to the electron‐withdrawing effect of carbonyl ligands on the iron nitride core. Described here is the synthesis and reactivity of Fe4(μ4‐N)(CO)8(CNArMes2)4]?, an electron‐rich analogue of Fe4(μ4‐N)(CO)12]?, where the interstitial nitride displays significant nucleophilicity. This characteristic enables rational expansion with main‐group and transition‐metal centers to yield unsaturated sites. The resulting clusters display surface‐like reactivity through coordination‐sphere‐dependent atom rearrangement and metal–metal cooperativity. |
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| Keywords: | cluster expansion isocyanides metal clusters metal surfaces nitrides |
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