The reaction of [IrH2Cl(PiPr3)2] (2) with the pentadiyne derivative HCCCCCPh2OH (1) yields the five‐coordinate compound [IrH(CCCCPh2OH)Cl(PiPr3)2] (3), which photochemically rearranges to give the vinylidene‐substituted isomer trans‐[IrCl(CCH‐CCPh2OH)(PiPr3)2] (4). On treatment of 3 with pyridine, the octahedral complex [IrH (CCCCPh2OH)Cl(py)(PiPr3)2] (5) is formed. While attempts to eliminate water from 4 (or 5) failed, the reaction of 3 with one equivalent of trifluorosulfonic acid anhydride and two equivalents of triethylamine led to the formation of trans‐[IrCl(CCCCCPh2)(PiPr3)2] (6), which is the first neutral transition‐metal complex containing a C5R2 ligand. The X‐ray structural analysis of 6 reveals a perfect square‐planar coordination geometry around the metal centre and an almost linear IrC5 chain with Ir‐CC and CCC bond angles of 174–179°.
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Lass et al. (1996) studied this question.
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