Year 2007, Month 10 (Section Full Articles, Page 1960)
Reaction of neodymium diiodide with methanol in acetonitrile. Structure of the cluster [Nd4(µ2-I)1.1(µ3-I)(µ2-OMe)4.9(µ4-O)(MeCN)12]I3
D. M. Kuzyaev, G. K. Fukin, E. V. Baranov, and M. N. Bochkarev
The reaction of neodymium diiodide NdI2 with excess methanol in acetonitrile produced the tetranuclear neodymium cluster [Nd4(µ2-I)1.1(µ3-I)(µ2-OMe)4.9(µ4-O)(MeCN)12]I3 (1). In the latter, the isomorphic substitution of one methoxy group by an I– anion with site occupancies (%) of 90 and 10, respectively, was observed. Due to the isomorphic substitution in the crystal, cluster 1 can be considered as a superposition of two complexes, [Nd4(µ2-I)(µ3I)(µ2-OMe)5(µ4-O)(MeCN)12]I3 and [Nd4(µ2-I)2(µ3-I)(µ2-OMe)4(µ4-O)(MeCN)12]I3. The characteristic feature of cluster 1 is that the center of the Nd4 cage is occupied by the µ4-coordinated O2– anion, which is indicative of the partial O—C bond cleavage in methanol. The reaction of NdI2 with an equimolar amount of MeOH in an acetonitrile solution produced methoxide NdI2(OMe)(MeCN)4 in 49% yield.
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