Within the reinvestigation of Ni–Sb carbonyl cluster chemistry, we report here the synthesis and characterization of the new [Ni19Sb4(CO)26]4– cluster and the synthesis, structure, magnetic characterization and electrical resistivity of the viologen salts of the previously known [Ni13Sb2(CO)24]n– (n = 2, 3) anionic species. The crystal structures of [NEt4]4 [Ni19Sb4(CO)26], [EtV]8[Ni13Sb2(CO)24]3·4DMF·2C6H14 and [EtV]3[Ni13Sb2(CO)24]·1.5THF (EtV = 1,1 -diethyl-4,4 -bipyridilium cation, DMF = N,N-dimethylformamide, THF = tetrahydrofuran) are described. Notably, the unit cell of [EtV]8[Ni13Sb2(CO)24]3·4DMF·2C6H14 involves a mixture of two [Ni13Sb2(CO)24]3– trianions and one [Ni13Sb2(CO)24]2– dianion, as it also contains eight [EtV]+· radical monocations, which are assembled in infinite stacks. In contrast, the unit cell of the [EtV]3[Ni13Sb2(CO)24]·1.5THF salt contains four [Ni13Sb2(CO)24]3– trianions along with twelve [EtV]+· radicalmonocations, four of which are arranged into two pairs of isolated dimers, whereas the other two sets of four form two infinite stacks that extend over the whole crystal. The charges of the miscellaneous ions have been assigned on the basis of electroneutrality and spectroscopic evidence. More specifically, the infrared spectra of [EtV]8[Ni13Sb2(CO)24]3· 4DMF·2C6H14, both in the solid state and in solution, clearly indicate the presence of a 2:1 mixture of [Ni13Sb2(CO)24]3– and [Ni13Sb2(CO)24]2– anions. Resistivity measurements performed on pellets of powdered samples indicate that the [EtV]8[Ni13Sb2(CO)24]3·4DMF·2C6H14 salt substantially behaves as an insulator. A study of the magnetic behaviour of [EtV]8[Ni13Sb2(CO)24]3·4DMF·2C6H14 evidences pairing among the electrons of the EtV+· molecules, in agreement with DFT calculations, and the odd-electron clusters behave as paramagnetic centres of spin S = 1.

The Chemistry of Ni-Sb Carbonyl Clusters - Synthesis and Characterization of the [Ni19Sb4(CO)26]4-Tetraanion and the Viologen Salts of [Ni13Sb2(CO)24]n-Carbonyl Clusters / Femoni, Cristina; Iapalucci, Maria Carmela; Longoni, Giuliano; Zacchini, Stefano; Ciabatti, Iacopo; Della Valle, Raffaele Guido; Mazzani, Marcello; Ricco', Mauro. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1434-1948. - 2014:25(2014), pp. 4151-4158. [10.1002/ejic.201402289]

The Chemistry of Ni-Sb Carbonyl Clusters - Synthesis and Characterization of the [Ni19Sb4(CO)26]4-Tetraanion and the Viologen Salts of [Ni13Sb2(CO)24]n-Carbonyl Clusters

MAZZANI, Marcello;RICCO', Mauro
2014-01-01

Abstract

Within the reinvestigation of Ni–Sb carbonyl cluster chemistry, we report here the synthesis and characterization of the new [Ni19Sb4(CO)26]4– cluster and the synthesis, structure, magnetic characterization and electrical resistivity of the viologen salts of the previously known [Ni13Sb2(CO)24]n– (n = 2, 3) anionic species. The crystal structures of [NEt4]4 [Ni19Sb4(CO)26], [EtV]8[Ni13Sb2(CO)24]3·4DMF·2C6H14 and [EtV]3[Ni13Sb2(CO)24]·1.5THF (EtV = 1,1 -diethyl-4,4 -bipyridilium cation, DMF = N,N-dimethylformamide, THF = tetrahydrofuran) are described. Notably, the unit cell of [EtV]8[Ni13Sb2(CO)24]3·4DMF·2C6H14 involves a mixture of two [Ni13Sb2(CO)24]3– trianions and one [Ni13Sb2(CO)24]2– dianion, as it also contains eight [EtV]+· radical monocations, which are assembled in infinite stacks. In contrast, the unit cell of the [EtV]3[Ni13Sb2(CO)24]·1.5THF salt contains four [Ni13Sb2(CO)24]3– trianions along with twelve [EtV]+· radicalmonocations, four of which are arranged into two pairs of isolated dimers, whereas the other two sets of four form two infinite stacks that extend over the whole crystal. The charges of the miscellaneous ions have been assigned on the basis of electroneutrality and spectroscopic evidence. More specifically, the infrared spectra of [EtV]8[Ni13Sb2(CO)24]3· 4DMF·2C6H14, both in the solid state and in solution, clearly indicate the presence of a 2:1 mixture of [Ni13Sb2(CO)24]3– and [Ni13Sb2(CO)24]2– anions. Resistivity measurements performed on pellets of powdered samples indicate that the [EtV]8[Ni13Sb2(CO)24]3·4DMF·2C6H14 salt substantially behaves as an insulator. A study of the magnetic behaviour of [EtV]8[Ni13Sb2(CO)24]3·4DMF·2C6H14 evidences pairing among the electrons of the EtV+· molecules, in agreement with DFT calculations, and the odd-electron clusters behave as paramagnetic centres of spin S = 1.
The Chemistry of Ni-Sb Carbonyl Clusters - Synthesis and Characterization of the [Ni19Sb4(CO)26]4-Tetraanion and the Viologen Salts of [Ni13Sb2(CO)24]n-Carbonyl Clusters / Femoni, Cristina; Iapalucci, Maria Carmela; Longoni, Giuliano; Zacchini, Stefano; Ciabatti, Iacopo; Della Valle, Raffaele Guido; Mazzani, Marcello; Ricco', Mauro. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1434-1948. - 2014:25(2014), pp. 4151-4158. [10.1002/ejic.201402289]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/2787075
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