The two clusters [HFe<sub>5</sub>NiN(CO)<sub>14</sub>]<sup>2-</sup> (1) and [HFe<sub>4</sub>Ni<sub>2</sub>N(CO)<sub>13</sub>]<sup>2-</sup> (2) were obtained by reaction of [Fe<sub>4</sub>N(CO)<sub>12</sub>]<sup>-</sup> and [Ni<sub>6</sub>(CO)<sub>12</sub>]<sup>2-</sup> in refluxing MeCN and EtCN, respectively, along with other Fe-Ni mixed metal clusters. Their solid state structures were determined on the [PPh<sub>4</sub>]<sup>+</sup> 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. © 2006 Elsevier B.V. All rights reserved.
DELLA PERGOLA, R., Fumagalli, A., Garlaschelli, L., Manassero, C., Manassero, M., Sansoni, M., et al. (2008). Iron-nickel mixed metal nitrido clusters: Synthesis and solid state structure of the anions [HFe5NiN(CO)14]2- and [HFe4Ni2N(CO)13]2-. INORGANICA CHIMICA ACTA, 361(5), 1763-1769 [10.1016/j.ica.2006.10.008].
Iron-nickel mixed metal nitrido clusters: Synthesis and solid state structure of the anions [HFe5NiN(CO)14]2- and [HFe4Ni2N(CO)13]2-
DELLA PERGOLA, ROBERTO;SIRONI, ANNALISA
2008
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. © 2006 Elsevier B.V. All rights reserved.
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