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Self-Assembly of Trinuclear Half-Sandwich Metal (Co and Ru) Complexes Containing Ancillary ortho-Carborane-1,2-dithiolato Ligands

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posted on 2008-03-24, 00:00 authored by Jia-Sheng Zhang, Shuang Liu, Guo-Liang Wang, Yue-Jian Lin, Guo-Xin Jin
One-step syntheses of cobalt- and ruthenium-based trinuclear complexes have been accomplished in high yields by a self-assembly strategy. Reaction of 16-electron “pseudoaromatic” half-sandwich cobalt complex [Cp*Co{S2C2(B10H10)}] (1) (Cp* = η5-pentamethylcyclopentadienyl) and ruthenium complex [(p-cymene)Ru{S2C2(B10H10)}] (2) with 2,4,6-tri-4-pyridyl-1,3,5-triazine (tpt) and 2,4,6-tri[(4-pyridyl)sulfanylmethyl]-1,3,5-triazine (tpst) in dichloromethane gave the corresponding multicluster complexes [Cp*Co{S2C2(B10H10)}]3(tpt) (3), [(p-cymene)Ru{S2C2(B10H10)}]3(tpt) (4), and [Cp*Co{S2C2(B10H10)}]3(tpst) (5), respectively. The X-ray structures of complexes 3 and 4 reveal that each tpt unit bridges three [Cp*Co{S2C2(B10H10)}] and [(p-cymene)Ru{S2C2(B10H10)}] fragments in a cis-conformation, respectively. However, three [Cp*Co{S2C2(B10H10)}] units in complex 5 are arranged in a trans-conformation. Single-crystal X-ray diffraction analyses also show that there are different packing patterns in complexes 35. Complexes 3 and 4 form two different channels by pairing up molecules, while complex 5 forms one-dimensional infinite chains through π−π stacking interactions.