The nitrido-encapsulated heterometallic cluster anions [Co 10Rh(N)2(CO)21]3- (1), [Co 10Rh2(N)2(CO)24]2- (2), and [Co11Rh(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 11N2(CO)11(μ2-CO) 10]3-, and 2, despite its even number of electrons, is a paramagnetic species. © 2007 American Chemical Society.
Costa, M., Della Pergola, R., Fumagalli, A., Laschi, F., Losi, S., Macchi, P., et al. (2007). Mixed Co-Rh nitrido-encapsulated carbonyl clusters. Synthesis, solid-state structure, and electrochemical/EPR characterization of the anions [Co 10Rh(N)2(CO)21]3-, [Co 10Rh2(N)2(CO)24]2-, and [Co11Rh(N)2(CO)24]2-. INORGANIC CHEMISTRY, 46(2), 552-560 [10.1021/ic0608288].
Mixed Co-Rh nitrido-encapsulated carbonyl clusters. Synthesis, solid-state structure, and electrochemical/EPR characterization of the anions [Co 10Rh(N)2(CO)21]3-, [Co 10Rh2(N)2(CO)24]2-, and [Co11Rh(N)2(CO)24]2-
Laschi, Franco;Zanello, Piero
2007-01-01
Abstract
The nitrido-encapsulated heterometallic cluster anions [Co 10Rh(N)2(CO)21]3- (1), [Co 10Rh2(N)2(CO)24]2- (2), and [Co11Rh(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 11N2(CO)11(μ2-CO) 10]3-, and 2, despite its even number of electrons, is a paramagnetic species. © 2007 American Chemical Society.File | Dimensione | Formato | |
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https://hdl.handle.net/11365/7009
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