Title: DFT Calculations of Cubane-Type Mo<sub>2</sub>Ru<sub>2</sub>S<sub>4</sub>Clusters. Stability of a Possible Dinitrogen Cluster and an Isolable Acetonitrile Cluster
Abstract: Abstract The electronic properties of cubane-type mixed-metal sulfido clusters with an Mo(V)2Ru(II)2S4 core and possible dinitrogen activation on it are described from DFT computations. The cluster [(CpRu)2{MoCl2(MeCN)}2(μ3-S)4] (Cp = η5-C5H5), whose Cp* analogue (Cp* = η5-C5Me5) was isolated and fully characterized by X-ray crystallographic analysis, has a closed-shell singlet ground state. Upon release of the acetonitrile ligands, the ground state remains in a closed-shell singlet state, the corresponding open-shell singlet and triplet states lying 2 kcal mol−1 above the closed-shell singlet state. Dinitrogen can hardly coordinate to this neutral [(CpRu)2(MoCl2)2(μ3-S)4] cluster. However, upon reduction by two electrons the binding energy for two N2 molecules to the resultant anionic cluster [(CpRu)2{MoCl2(N2)}2(μ3-S)4]2− increases to 4 kcal mol−1. This interaction, which still seems too weak to become isolable, is analyzed in terms of molecular orbitals to increase our understanding of dinitrogen activation by synthetic systems. The HOMO of [(CpRu)2(MoCl2)2(μ3-S)4]2− is pointing toward missing ligands and can interact effectively with the πg* orbitals of dinitrogen. This orbital might play a role in the binding of dinitrogen.
Publication Year: 2006
Publication Date: 2006-01-01
Language: en
Type: article
Indexed In: ['crossref']
Access and Citation
Cited By Count: 6
AI Researcher Chatbot
Get quick answers to your questions about the article from our AI researcher chatbot