Magnetic behavior of odd- and even-electron metal carbonyl clusters: the case study of [Co(8)Pt(4)C(2)(CO)(24)](n-) (n = 1, 2) carbide cluster

Cristina Femoni; Maria Carmela Iapalucci; Giuliano Longoni; Joanna Wolowska; Stefano Zacchini; Piero Zanello; Serena Fedi; Mauro Riccò; Daniele Pontiroli; Marcello Mazzani

doi:10.1021/ja907608c

Magnetic behavior of odd- and even-electron metal carbonyl clusters: the case study of [Co(8)Pt(4)C(2)(CO)(24)](n-) (n = 1, 2) carbide cluster

J Am Chem Soc. 2010 Mar 10;132(9):2919-27. doi: 10.1021/ja907608c.

Authors

Cristina Femoni¹, Maria Carmela Iapalucci, Giuliano Longoni, Joanna Wolowska, Stefano Zacchini, Piero Zanello, Serena Fedi, Mauro Riccò, Daniele Pontiroli, Marcello Mazzani

Affiliation

¹ Dipartimento di Chimica Fisica e Inorganica, Università di Bologna, Viale Risorgimento 4-40136 Bologna, Italy.

PMID: 20146466
DOI: 10.1021/ja907608c

Abstract

The reaction of [Co(6)C(CO)(15)](2-) with 2 equiv of PtCl(2)(Et(2)S)(2) affords the new heterobimetallic [Co(8)Pt(4)C(2)(CO)(24)](2-), [1](2-), carbonyl cluster. [1](2-) undergoes reversible chemical and electrochemical oxidation and reduction processes disclosing a complete series of [1](n-) (n = 1-4) clusters. The mono- and dianion of [1](n-) have been isolated as their tetra-substituted ammonium salts and fully characterized by means of IR, (13)C NMR, ESI-MS, and X-ray crystallography. Variable-temperature (VT) solid-state EPR studies on pure crystalline samples indicate that both [1](2-) and [1](-*) are paramagnetic, due to a doublet state of the latter and a triplet state of [1](2-). This conclusion is supported by SQUID measurements on the same crystalline sample of [1](2-). The present study indisputably demonstrates that even-electron transition metal carbonyl clusters (TMCC) can be magnetic.