Mixed Co-Rh nitrido-encapsulated carbonyl clusters. synthesis, solid-state structure, and electrochemical/EPR characterization of the anions [Co10Rh(N)2(CO)21]3-, [Co10Rh2(N)2(CO)24]2-, and [Co11Rh(N)2(CO)24]2-

Michela Costa; Roberto Della Pergola; Alessandro Fumagalli; Franco Laschi; Serena Losi; Piero Macchi; Angelo Sironi; Piero Zanello

doi:10.1021/ic0608288

Mixed Co-Rh nitrido-encapsulated carbonyl clusters. synthesis, solid-state structure, and electrochemical/EPR characterization of the anions [Co10Rh(N)2(CO)21]3-, [Co10Rh2(N)2(CO)24]2-, and [Co11Rh(N)2(CO)24]2-

Inorg Chem. 2007 Jan 22;46(2):552-60. doi: 10.1021/ic0608288.

Authors

Michela Costa¹, Roberto Della Pergola, Alessandro Fumagalli, Franco Laschi, Serena Losi, Piero Macchi, Angelo Sironi, Piero Zanello

Affiliation

¹ Dipartimento di Biologia Strutturale e Funzionale dell'Università degli Studi dell'Insubria, Via J. H. Dunant 3, 21100 Varese, Italy.

PMID: 17279835
DOI: 10.1021/ic0608288

Abstract

The nitrido-encapsulated heterometallic cluster anions [Co(10)Rh(N)2(CO)21](3-) (1), [Co(10)Rh2(N)2(CO)24](2-) (2), and [Co(11)Rh(N)2(CO)24](2-) (3) have been obtained by tailored redox-condensation reactions. These three anions are rare high-nuclearity mixed-metal clusters containing two interstitial nitrogen atoms. Their structures have been determined by single-crystal X-ray diffraction on their [NR4]+ salts (R = Me for 1 and 3, R = Et for 2), and their electrochemical and ESR properties have been studied in detail. It is noteworthy that 1 has an unprecedented stereochemistry that does not exhibit a close geometrical resemblance with the isoelectronic homometallic anion [Co(11)N2(CO)11(mu2-CO)10](3-), and 2, despite its even number of electrons, is a paramagnetic species.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Cobalt / chemistry*
Crystallography, X-Ray
Electrochemistry
Electron Spin Resonance Spectroscopy
Models, Molecular
Rhodium / chemistry*

Substances

Cobalt
Rhodium