Controlled Expansion of a Strong‐Field Iron Nitride Cluster: Multi‐Site Ligand Substitution as a Strategy for Activating Interstitial Nitride Nucleophilicity

Drance, Myles J.; Mokhtarzadeh, Charles C.; Melaimi, Mohand; Agnew, Douglas W.; Moore, Curtis E.; Rheingold, Arnold L.; Figueroa, Joshua S.

doi:10.1002/ange.201801206

Title: Controlled Expansion of a Strong‐Field Iron Nitride Cluster: Multi‐Site Ligand Substitution as a Strategy for Activating Interstitial Nitride Nucleophilicity

Journal Article · Thu May 24 00:00:00 EDT 2018 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201801206· OSTI ID:1438949

Drance, Myles J. ^[1]; Mokhtarzadeh, Charles C. ^[1]; Melaimi, Mohand ^[2]; Agnew, Douglas W. ^[1]; Moore, Curtis E. ^[1]; Rheingold, Arnold L. ^[1];

^[1]

Department of Chemistry and Biochemistry University of California, San Diego 9500 Gilman Drive MC 0358 La Jolla CA 92093 USA
UCSD-CNRS Joint Research Laboratory (UMI 3555) Department of Chemistry and Biochemistry University of California, San Diego 9500 Gilman Drive, Mail Code 0358 La Jolla California 92093 USA

Abstract 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.

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Sponsoring Organization:: USDOE

OSTI ID:: 1438949

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 130 Journal Issue: 40; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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