Iron-nickel mixed metal nitrido clusters: Synthesis and solid state structure of the anions [HFe5NiN(CO)14] and [HFe4Ni2N(CO)13] |
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Authors: | Roberto Della Pergola Alessandro Fumagalli Carlo Manassero Mirella Sansoni |
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Institution: | a Dipartimento di Scienze dell’Ambiente e del Territorio, Università degli Studi di Milano Bicocca, Piazza della Scienza 1, 20126 Milano, Italy b Dipartimento di Biologia Strutturale e Funzionale, Università degli studi dell’Insubria, Via J. H. Dunant 3, 21100 Varese, Italy c Dipartimento di Chimica Inorganica, Metallorganica ed Analitica, Via G. Venezian 21, 20133 Milano, Italy d Dipartimento di Chimica Strutturale e Stereochimica Inorganica, Via G. Venezian 21, 20133 Milano, Italy |
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Abstract: | The two clusters HFe5NiN(CO)14]2− (1) and HFe4Ni2N(CO)13]2− (2) were obtained by reaction of Fe4N(CO)12]− and Ni6(CO)12]2− in refluxing MeCN and EtCN, respectively, along with other Fe-Ni mixed metal clusters. Their solid state structures were determined on the PPh4]+ salts, and both have an octahedral metal cage, containing an interstitial nitrogen atom. The two Ni atoms in 2 are cis, with a Ni-Ni separation of 2.724(1) Å. The two anions have different stereochemistry of the carbonyl ligands: in 1, five CO’s are semi-bridging, and the remaining nine are terminal; in 2 there are three asymmetric bridging and ten terminal ligands (two for each iron and one for each nickel). The hydride ligands were located in the final difference maps, both bridging a Ni-Fe edge of the clusters but, thanks to the better quality of the diffraction data, the metal-hydrogen distances were refined only in 2. In this cluster, the Fe-H and Ni-H bond lengths are 1.77(2) and 1.79(2) Å, respectively. |
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Keywords: | Nickel Iron Heterometallic cluster Nitride Bridging hydride Interstitial nitrogen atom |
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