TY - JOUR
T1 - DFT calculations of cubane-type Mo2Ru2S4 clusters. Stability of a possible dinitrogen cluster and an isolable acetonitrile cluster
AU - Yoshizawa, Kazunari
AU - Kihara, Naoki
AU - Shiota, Yoshihito
AU - Seino, Hidetake
AU - Mizobe, Yasushi
PY - 2006/11/7
Y1 - 2006/11/7
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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U2 - 10.1246/bcsj.79.53
DO - 10.1246/bcsj.79.53
M3 - Article
AN - SCOPUS:33750494325
VL - 79
SP - 53
EP - 58
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
SN - 0009-2673
IS - 1
ER -