Publication8

The thermolysis of [(Cp*Mo)2B4H 4S2], 1 with [Fe2(CO)9] yielded eleven vertex dimolybdathiaborane cluster [(Cp*Mo)2B 4H2S2Fe4(CO)9(μ-CO)], 2 together with cubane-type [(Cp*Mo)2(μ3-S) 2B2H(μ-H){Fe(CO)2}2Fe(CO) 3], 3 and a fused cluster [(Cp*Mo)2B 4H4S2 Fe2(CO)5], 4. In a similar fashion, thermolysis of [(Cp*Mo)2B4H 4Se2], 5 with [Fe2(CO)9] yielded tetracapped pentagonal bipyramidal [(Cp*Mo)2B3H 3Se2{Fe(CO)2}2{Fe(CO) 3}2], 6, and an incomplete cubane-type cluster [(Cp*Mo)2BH(μ3-Se)2Fe 2(CO)7], 7. In parallel with the formation of 6 and 7, clusters [(Cp*Mo)2(μ3-Se)2B 2H(μ-H){Fe(CO)2}2Fe(CO)3], 8 and [(Cp*Mo)2B4 H4Se2Fe 2(CO)5], 9 were obtained albeit in low isolated yields. Cluster 6 exhibits tetracapped pentagonal bipyramidal geometry, having 98 cluster valence electrons, appropriate for its geometric structure. The thermolysis of 9 in presence of [Co2(CO)8] led to the isolation of [(Cp*Mo)2B3H2Se 2Co(CO)(μ-CO)3{Fe4(CO)7}], 10. The structure analysis shows that both of the clusters 2 and 10 are based on 11-vertex closo-cage geometry and the core geometry of them can be derived from tricapped square antiprism by performing diamond-square-diamond (dsd) rearrangement. All new metallaheteroborane compounds have been fully characterized by various spectroscopic techniques and elemental analyses and the geometric structures were unequivocally established by crystallographic analysis of 2, 6, 7 and 10. © 2012 Elsevier B.V. All rights reserved.