Coordination and Hydroboration of Ru(II)-Borate Complexes: Dihydridoborate vs. Bis(dihydridoborate) |
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| Authors: | Kriti Pathak Sourav Gayen Suvam Saha Chandan Nandi Shivankan Mishra Prof. Dr. Sundargopal Ghosh |
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| Affiliation: | 1. Department of Chemistry, Indian Institute of Technology, Madras, Chennai, 600036 India;2. Department of Chemistry, Indian Institute of Technology, Madras, Chennai, 600036 India These authors contributed equally to this work. |
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| Abstract: | Treatment of [Cp*RuCl2]2, 1 , [(COD)IrCl]2, 2 or [(p-cymene)RuCl2]2, 3 (Cp*=η5-C5Me5, COD= 1,5-cyclooctadiene and p-cymene=η6-iPrC6H4Me) with heterocyclic borate ligands [Na[(H3B)L], L1 and L2 ( L1 : L=amt, L2 : L=mp; amt=2-amino-5-mercapto-1,3,4-thiadiazole, mp=2-mercaptopyridine) led to the formation of borate complexes having uncommon coordination. For example, complexes 1 and 2 on reaction with L1 and L2 afforded dihydridoborate species [LAM(μ-H)2BHL] 4 – 6 ( 4 : LA=Cp*, M=Ru, L=amt; 5 : LA=Cp*, M=Ru, L=mp; 6 : LA=COD, M=Ir, L=mp). On the other hand, treatment of 3 with L2 yielded cis- and trans-bis(dihydridoborate) species, [Ru{(μ-H)2BH(mp)}2], cis- 7 and trans- 7 . The isolation and structural characterization of fac- and mer-[Ru{(μ-H)2BH(mp)}{(μ-H)BH(mp)2}], 8 from the same reaction offered an insight into the behaviour of these dihydridoborate species in solution. Fascinatingly, despite having reduced natural charges on Ru centres both at cis-and trans- 7 , they underwent hydroboration reaction with alkynes that yielded both Markovnikov and anti-Markovnikov addition products, 10 a – d . |
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| Keywords: | alkene-borane ancillary ligand dihydridoborate hydroboration ruthenium |
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