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Controlled Expansion of a Strong‐Field Iron Nitride Cluster: Multi‐Site Ligand Substitution as a Strategy for Activating Interstitial Nitride Nucleophilicity
Author(s) -
Drance Myles J.,
Mokhtarzadeh Charles C.,
Melaimi Mohand,
Agnew Douglas W.,
Moore Curtis E.,
Rheingold Arnold L.,
Figueroa Joshua S.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201801206
Subject(s) - chemistry , nitride , reactivity (psychology) , iron nitride , ligand (biochemistry) , nucleophile , cooperativity , metal , coordination sphere , cluster (spacecraft) , crystallography , photochemistry , stereochemistry , catalysis , organic chemistry , receptor , medicine , biochemistry , alternative medicine , pathology , layer (electronics) , computer science , programming language
Multimetallic clusters have long been investigated as molecular surrogates for reactive sites on metal surfaces. In the case of the μ 4 ‐nitrido cluster [Fe 4 (μ 4 ‐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 [Fe 4 (μ 4 ‐N)(CO) 8 (CNAr Mes2 ) 4 ] − , an electron‐rich analogue of [Fe 4 (μ 4 ‐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.