The anion [Co13N2(CO)24]3-(1) has been obtained by pyrolisis at 100°C of [Co14N3(CO)26]3-(K+salt) in buffered water solution (pH 11). The X-ray crystal structure ([NMe4]+salt) revealed that the metal cage of the anion is composed by a three-layered polyhedron with the two nitrides in trigonal prismatic environments. Anion 1, with 178 cluster valence electrons (CVE), is isostructural with the carbido species [Co13C2(CO)24]3-(2, 176 CVE) and [Co13C2(CO)24]4-(3, 177 CVE). In acetonitrile solution 1 undergoes two reversible one-electron additions. Comparison with the dicarbido tetraanion 3 evidences that the two clusters do not display isoelectronic redox paths. Actually, [Co13N2(CO)24]n-undergoes the three-membered redox sequence (n=3-5) from 178 to 180 CVE, whereas [Co13C2(CO)24]m-undergoes the four-membered series (m=3-6), from 176 to 179 CVE. The different redox behaviour and the minor differences in the Co-Co bond distances point out that carbide and nitride have different role in stabilizing the two compounds. © 2003 Elsevier Science B.V. All rights reserved.

Synthesis, structural and electrochemical characterization of the nitrido-carbonyl cluster anion [Co13N2(CO)24]3-. The different redox propensity of the two isostructural families [Co13N2(CO)24]n-and [Co13C2(CO)24]m-

Macchi, Piero;
2003-01-01

Abstract

The anion [Co13N2(CO)24]3-(1) has been obtained by pyrolisis at 100°C of [Co14N3(CO)26]3-(K+salt) in buffered water solution (pH 11). The X-ray crystal structure ([NMe4]+salt) revealed that the metal cage of the anion is composed by a three-layered polyhedron with the two nitrides in trigonal prismatic environments. Anion 1, with 178 cluster valence electrons (CVE), is isostructural with the carbido species [Co13C2(CO)24]3-(2, 176 CVE) and [Co13C2(CO)24]4-(3, 177 CVE). In acetonitrile solution 1 undergoes two reversible one-electron additions. Comparison with the dicarbido tetraanion 3 evidences that the two clusters do not display isoelectronic redox paths. Actually, [Co13N2(CO)24]n-undergoes the three-membered redox sequence (n=3-5) from 178 to 180 CVE, whereas [Co13C2(CO)24]m-undergoes the four-membered series (m=3-6), from 176 to 179 CVE. The different redox behaviour and the minor differences in the Co-Co bond distances point out that carbide and nitride have different role in stabilizing the two compounds. © 2003 Elsevier Science B.V. All rights reserved.
2003
Cobalt carbonyl cluster; Electrochemistry; Interstitial nitride; X-ray crystallography; Physical and Theoretical Chemistry; Inorganic Chemistry; Materials Chemistry2506 Metals and Alloys
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11311/1063439
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