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-.
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.
Costa
Michela
M
Dipartimento di Biologia Strutturale e Funzionale dell'Università degli Studi dell'Insubria, Via J. H. Dunant 3, 21100 Varese, Italy.
Pergola
Roberto Della
RD
Fumagalli
Alessandro
A
Laschi
Franco
F
Losi
Serena
S
Macchi
Piero
P
Sironi
Angelo
A
Zanello
Piero
P
D003035:Cobalt / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004563:Electrochemistry; D004578:Electron Spin Resonance Spectroscopy; D008958:Models, Molecular; D012238:Rhodium / Q000737:chemistry*
D003035:Cobalt; D012238:Rhodium