DFT calculations of cubane-type Mo2Ru2S4 clusters. Stability of a possible dinitrogen cluster and an isolable acetonitrile cluster

Kazunari Yoshizawa, Naoki Kihara, Yoshihito Shiota, Hidetake Seino, Yasushi Mizobe

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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)}23-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)23-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)}23-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) 23-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.

Original languageEnglish
Pages (from-to)53-58
Number of pages6
JournalBulletin of the Chemical Society of Japan
Volume79
Issue number1
DOIs
Publication statusPublished - Nov 7 2006

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Discrete Fourier transforms
Ground state
Chemical activation
Ligands
Molecular orbitals
Binding energy
Electronic properties
Metals
X rays
Molecules
Electrons
acetonitrile

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

DFT calculations of cubane-type Mo2Ru2S4 clusters. Stability of a possible dinitrogen cluster and an isolable acetonitrile cluster. / Yoshizawa, Kazunari; Kihara, Naoki; Shiota, Yoshihito; Seino, Hidetake; Mizobe, Yasushi.

In: Bulletin of the Chemical Society of Japan, Vol. 79, No. 1, 07.11.2006, p. 53-58.

Research output: Contribution to journalArticle

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N2 - 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.

AB - 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.

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