Hume-rothery phase-inspired metal-rich molecules: Cluster expansion of [Ni(ZnMe)6(ZnCp2] by face capping with Ni06-toluene) and NiI5-Cp)

Mariusz Molon, Christian Gemel, Paul Jerabek, Lukas Trombach, Gernot Frenking, Roland A. Fischer

Research output: Contribution to journalArticlepeer-review

12 Scopus citations


The novel all-hydrocarbon ligand-stabilized binuclear clusters of metal-core composition Ni2Zn7E, [(η5-Cp)Ni2(ZnMe)6(ZnCp)(ECp)] (1-Zn, E = Zn; 1-Ga, E = Ga) and [(η6-toluene)Ni2(ZnCp)2(ZnMe)6] (2; Cp∗ = pentamethylcyclopentadienyl), were obtained via Ga/Zn and Al/Zn exchange reactions using the starting compounds [Ni2(ECp)32-C2H4)2] (E = Al/Ga) and an excess of ZnMe2 (Me = CH3). Compounds 1-Zn and 1-Ga are very closely related and differ only by one Zn or Ga atom in the group 12/13 metal shell (Zn/Ga) around the two Ni centers. Accordingly, 1-Zn is EPR-active and 1-Ga is EPR-silent. The compounds were derived as a crystalline product mixture. All new compounds were characterized by 1H and 13C NMR and electron paramagnetic resonance (EPR) spectroscopy, mass spectrometric analysis using liquid-injection field desorption ionization, and elemental analysis, and their molecular structures were determined by single-crystal X-ray diffraction studies. In addition, the electronic structure has been investigated by DFT and QTAIM calculations, which suggest that there is a Ni1-Ni2 binding interaction. Similar to Zn-rich intermetallic phases of the Hume-Rothery type, the transition metals (here Ni) are distributed in a matrix of Zn atoms to yield highly Zn-coordinated environments. The organic residues, ancillary ligands (Me, Cp, and toluene), can be viewed as the "protecting" shell of the 10-metal-atom core structures. The soft and flexible binding properties of Cp∗ and transferability of Me substituents between groups 12 and 13 are essential for the success of this precedence-less type of cluster formation reaction.

Original languageEnglish
Pages (from-to)10403-10411
Number of pages9
JournalInorganic Chemistry
Issue number19
StatePublished - 6 Oct 2014
Externally publishedYes


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