Six metal carbido−carbonyl clusters have been isolated and recognized as members of a multivalent family based on the dioctahedral Rh10(C)2 frame, with variable numbers of CO ligands, AuPPh3 moieties, and anionic charge: [Rh10(C)2(CO)x(AuPPh3)y]n− (x = 18, 20; y = 4, 5, 6; n = 0, 1, 2). Anions [Rh10(C)2(CO)18(AuPPh3)4]− ([2]−) and [Rh10(C)2(CO)18(AuPPh3)4]2− ([2]2−) have been obtained by the reduction of [Rh10(C)2(CO)18(AuPPh3)4] (2) under N2,while [Rh10(C)2(CO)18(AuPPh3)5]− ([3]−) was obtained from [Rh10(C)2(CO)20(AuPPh3)4] (1) by reduction under a CO atmosphere. [3]− can be better obtained by the addition of AuPPh3Cl to [2]2−. [Rh10(C)2(CO)18(AuPPh3)6] (4) is obtained from [3]− and 2 as well by the reduction and subsequent addition of AuPPh3Cl. The molecular structures of [2]2− ([NBu4]+ salt), [3]− ([NMe4]+ salt), and 4 have been determined by single-crystal X-ray diffraction. The redox activities of complexes 1, 2 and [3]− have been investigated by electrochemical and electron paramagnetic resonance (EPR) techniques. The data from EPR spectroscopy have been accounted for by theoretical calculations.

Cherchi, L., Fumagalli, A., Fedi, S., Zanello, P., FABRIZI DE BIANI, F., Laschi, F., et al. (2012). Synthesis, reactivity, electrochemical behavior, and crystal structure of a family of multivalent metal carbido–carbonyl clusters based on the Rh10(C)2Au4–6 framework. INORGANIC CHEMISTRY, 51, 9171-9180 [10.1021/ic201613j].

Synthesis, reactivity, electrochemical behavior, and crystal structure of a family of multivalent metal carbido–carbonyl clusters based on the Rh10(C)2Au4–6 framework

FEDI, SERENA;ZANELLO, PIERO;FABRIZI DE BIANI, FABRIZIA;LASCHI, FRANCO;
2012

Abstract

Six metal carbido−carbonyl clusters have been isolated and recognized as members of a multivalent family based on the dioctahedral Rh10(C)2 frame, with variable numbers of CO ligands, AuPPh3 moieties, and anionic charge: [Rh10(C)2(CO)x(AuPPh3)y]n− (x = 18, 20; y = 4, 5, 6; n = 0, 1, 2). Anions [Rh10(C)2(CO)18(AuPPh3)4]− ([2]−) and [Rh10(C)2(CO)18(AuPPh3)4]2− ([2]2−) have been obtained by the reduction of [Rh10(C)2(CO)18(AuPPh3)4] (2) under N2,while [Rh10(C)2(CO)18(AuPPh3)5]− ([3]−) was obtained from [Rh10(C)2(CO)20(AuPPh3)4] (1) by reduction under a CO atmosphere. [3]− can be better obtained by the addition of AuPPh3Cl to [2]2−. [Rh10(C)2(CO)18(AuPPh3)6] (4) is obtained from [3]− and 2 as well by the reduction and subsequent addition of AuPPh3Cl. The molecular structures of [2]2− ([NBu4]+ salt), [3]− ([NMe4]+ salt), and 4 have been determined by single-crystal X-ray diffraction. The redox activities of complexes 1, 2 and [3]− have been investigated by electrochemical and electron paramagnetic resonance (EPR) techniques. The data from EPR spectroscopy have been accounted for by theoretical calculations.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11365/43619
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