Synthesis and structure of metallacarboranes bearing carborane-fused cyclopentenyl and dicarbollyl-fused cyclopentene ligands

New types of ligands, carborane-fused cyclopentenyl and dicarbollyl-fused cyclopentene, were conveniently prepared in high yields. Treatment of the lithium salt of carborane-fused cyclopentenyl anion, [1,2-[C(Me)CHC(Ph)]-1,2-C2B10H10]Li, with [Cp*RuCl](4) generated an 18-electron complex [eta(3):eta(2)-(PhCCHCMe)C2B10H10]Ru(eta(5)-Cp*). On the other hand, reaction of the dicarbollide salt, [7,8-(CH2CH 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 CMe)-7,8-C2B9H9]Na-2 with [(eta(6)-p-cymene)RuCl2](2) or CoCl2/CpNa, afforded the salt metathesis product [eta(5)-(CH2CH CMe)C2B9H9]Ru(eta(6)-p-cymene) or [eta(5)-(CH2CH CMe)C2B9H9]Co(eta(5)-C5H5) in good yields. In contrast, [7,8-(CH2CH CMe)-7,8-C2B9H9]Na-2 reacted with Ni(dppp)Cl-2 (dppp = 1,3-bis(diphenylphosphino)propane) to give another 18-electron metallacarborane [eta(5)-(CH2CH CMe)C2B9H9]Ni(dppp), in which one of the cage carbon atoms has been isomerized to the lower belt of the cage due to steric reasons. All these new metallacarborane compounds were fully characterized by NMR spectroscopy, high-resolution mass spectroscopy and single-crystal X-ray analyses.

Automated summary

New types of ligands, carborane-fused cyclopentenyl and dicarbollyl-fused cyclopentene, were conveniently prepared in high yields. These new metallacarborane compounds were fully characterized by NMR spectroscopy, high-resolution mass spectroscopy, and single-crystal X-ray analyses, showcasing their potential for further study in the field of organometallic chemistry.