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- |
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Authors: | Costa Michela Pergola Roberto Della Fumagalli Alessandro Laschi Franco Losi Serena Macchi Piero Sironi Angelo Zanello Piero |
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Institution: | Dipartimento di Biologia Strutturale e Funzionale dell'Università degli Studi dell'Insubria, Via J. H. Dunant 3, 21100 Varese, Italy. |
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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. |
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