The reaction of [Co6C(CO)15]2- with two equivalents of PtCl2(Et2S)2 affords the new heterobimetallic carbonyl cluster [Co8Pt4C2(CO)24]2-. Such a dianion undergoes reversible chemical and electrochemical oxidation and reduction processes disclosing a complete series of [Co8Pt4C2(CO)24]n- (n = 1-4) clusters. The mono- and dianions have been isolated as their tetra-substituted ammonium salts and fully characterized by means of IR, 13C NMR, ESI-MS, and X-ray crystallography. Variable-temperature (VT) solid-state EPR studies on pure crystalline samples indicate that both [Co8Pt4C2(CO)24]2- and [Co8Pt4C2(CO)24]-• are paramagnetic, due to a doublet state of the latter and a triplet state of [Co8Pt4C2(CO)24]2-. This conclusion is supported by SQUID measurements on the same crystalline sample of [Co8Pt4C2(CO)24]2-. The present study indisputably demonstrates that even-electron transition metal carbonyl clusters (TMCC) can be magnetic.

C., F., M. C., I., G., L., J., W., S., Z., Zanello, P., et al. (2010). MAGNETIC BEHAVIOR OF ODD- AND EVEN-ELECTRON METAL CARBONYL CLUSTERS: THE CASE STUDY OF [Co8Pt4C2(CO)24]n− ( n = 1, 2) CARBIDE CLUSTER. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 132, 2919-2927.

MAGNETIC BEHAVIOR OF ODD- AND EVEN-ELECTRON METAL CARBONYL CLUSTERS: THE CASE STUDY OF [Co8Pt4C2(CO)24]n− ( n = 1, 2) CARBIDE CLUSTER

ZANELLO, PIERO;
2010

Abstract

The reaction of [Co6C(CO)15]2- with two equivalents of PtCl2(Et2S)2 affords the new heterobimetallic carbonyl cluster [Co8Pt4C2(CO)24]2-. Such a dianion undergoes reversible chemical and electrochemical oxidation and reduction processes disclosing a complete series of [Co8Pt4C2(CO)24]n- (n = 1-4) clusters. The mono- and dianions have been isolated as their tetra-substituted ammonium salts and fully characterized by means of IR, 13C NMR, ESI-MS, and X-ray crystallography. Variable-temperature (VT) solid-state EPR studies on pure crystalline samples indicate that both [Co8Pt4C2(CO)24]2- and [Co8Pt4C2(CO)24]-• are paramagnetic, due to a doublet state of the latter and a triplet state of [Co8Pt4C2(CO)24]2-. This conclusion is supported by SQUID measurements on the same crystalline sample of [Co8Pt4C2(CO)24]2-. The present study indisputably demonstrates that even-electron transition metal carbonyl clusters (TMCC) can be magnetic.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11365/26903
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