Polyhedral iridathiaborane chemistry. Reactions of nido-6-SB9H11 and of [arachno-6-SB9H12]– with [{Ir(η5-C5Me5)Cl2}2] to give nido-8,7-iridathiaundecarboranes. A nuclear magnetic resonance and structural study

Abstract

The reaction of [{Ir(η⁵-C₅Me₅)Cl₂}₂] with nido-6-SB₉H₁₁ and a non-nucleophilic base yields [8-(η⁵-C₅Me₅)-nido-8,7-IrSB₉H₁₁]1, whereas with the [arachno-6-SB₉H₁₂]^– anion it yields [8-(η⁵-C₅Me₅)-9-Cl-nido-8,7-IrSB₉H₁₀]2, [8-(η⁵-C₅Me₅)-10-Cl-nido-8,7-IrSB₉H₁₀]3 and [1-(η⁵-C₅Me₅)-closo-1,2-IrSB₉H₉]4. With [Ir(CO)Cl(PPh₃)₂], Cs[B₉H₁₂] yields a compound formulated as [exo-9-{Cl-trans-(PPh₃)₂-cis-H₂Ir}-arachno-6-SB₉H₁₁] which, on thermolysis, yields 9-(PPh₃)-arachno-6-SB₉H₁₁. The crystal and molecular structures of Cs[arachno-6-SB₉H₁₂] and compound 2 have been established by single-crystal X-ray diffraction analysis, and all the iridathiaboranes have been examined in detail by ¹H and ¹¹B single and multiple magnetic resonance spectroscopy.