Reactions of carbon disulfide with open nido-6-iridadecaboranes. The formation of closed ten-vertex cluster compounds with boron-to-metal dithioformate bridges and a novel isocloso→closo cluster conversion
Abstract
The compounds [6-H-6,6-(PPh3)2-nido-6-IrB9H13]1 or [6-H-6-(PPh3)-6-(o-Ph2P[graphic omitted]]2 reacted with refluxing CS2 to form respectively [2,10-(PPh3)2-2,6;2,9-(µ-S2CH)2-closo-2-IrB9H6]4(14%) or [10-(PPh3)-2,6;2,9-(µ-S2CH)2-2-(o-Ph 2[graphic omitted]]5(17%). Compound 5(37%) was also obtained from CS2 and [1-H-1-(PPh3)-1-(o-Ph2P[graphic omitted]]3 in an unprecedented isocloso→closo conversion. The new compounds 4 and 5 are characterised by NMR spectroscopy, mass spectrometry and a single-crystal X-ray diffraction analysis on 4. Compound 4 has a conventional closo ten-vertex {2-IrB9} cluster structure with two SCHS units that bridge symmetrically from the iridium atom to the boron cluster at B(6) and B(9). Compound 5 has the same cluster structure, but now the metal-bound triarylphosphine is ortho-cycloboronated to B(1).