Structural Diversity Within the Series of 68-Electron M4L n E2 (L = 2-Electron Ligand; M = Fe, Ru, Os, Co; E = CH, N, P, NR, PR, S) Organometallic Clusters: A Theoretical Investigation

• DOI: 10.1007/s10876-012-0492-9
• Publication Date: 2012-05-23T04:10:33Z
• Authors: Nabila Guechtouli; Abdou Boucekkine; Jean-François Halet; Samia Kahlal; Hacène Meghezzi; Jean-Yves Saillard
• Keywords: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry; Organometallic clusters; DFT; 01 natural sciences; Mixed metal/main group; Skeletal isomerism; 0104 chemical sciences

Four different skeletal structural arrangements with very different connectivities are known for 6-vertex/68-electron of M4E2 core (M = transition metal; E = main-group atom or ligand). DFT calculations on a large number of title model compounds allow to rationalize the preferences between these structural shapes with respect to the nature of the metal and main-group elements constituting the cluster cage. In particular, the electronegativity of M and the “size” (first-row vs. second-row element) of E play an important role in the stability preference of a particular isomer. For several compounds, although only one type of structure is known, other low-energy isomeric forms are also likely to exist. Moreover, two structural types, so far unreported, are predicted to be stable enough for being synthesized.