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Angew Chem Int Ed Engl. 2018 Oct 1;57(40):13057-13061. doi: 10.1002/anie.201801206. Epub 2018 May 24.

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

Author information

1
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA, 92093, USA.
2
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 μ4 -nitrido cluster [Fe44 -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 [Fe44 -N)(CO)8 (CNArMes2 )4 ]- , an electron-rich analogue of [Fe44 -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.

KEYWORDS:

cluster expansion; isocyanides; metal clusters; metal surfaces; nitrides

PMID:
29719103
DOI:
10.1002/anie.201801206

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