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Selective Synthesis of Iridium(III) End-Capped Polyynes by Oxidative Addition of 1-Iodopolyynes to Vaska’s Complex

Abstract

The reaction of bis(triphenylphosphine)iridium(I) carbonyl chloride (Vaska’s complex) with a series of 1-iodopolyynes (1-CnI and 2-CnI) gave σ-polyynyl iridium(III) complexes with general formula R(C≡C)nIr(PPh3)2(Cl)(I)(CO). The use of acetonitrile as a solvent appeared crucial and allowed to selectively obtain only one from a few possible isomers. X-ray single crystal diffraction experiment for 2-C4[Ir]I allowed to determine the exact structure of this complex. Further spectroscopic measurements, especially 31P NMR, confirmed formation of the same type of isomers with trans coordinated phosphines in each case. All complexes were fully characterized with the use of NMR (1H, 13C and 31P), IR, UV/Vis, cyclic voltammetry and (ESI)HRMS techniques. Moreover, DFT calculations were performed for all the resulting species. The complexes with linear carbon chain from butadiyne to decapentayne are the longest iridium end-capped polyynes known to date since only compounds with (C≡C)2 structural motif have been reported so far. Moreover, we confirmed that the synthetic approach, first used for palladium(II) end-capped polyynes, may be also applied for the synthesis of other structurally new organometallic polyynes.

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Publication details

The article was received on 22 Oct 2018, accepted on 08 Nov 2018 and first published on 08 Nov 2018


Article type: Paper
DOI: 10.1039/C8DT04219E
Citation: Dalton Trans., 2018, Accepted Manuscript
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    Selective Synthesis of Iridium(III) End-Capped Polyynes by Oxidative Addition of 1-Iodopolyynes to Vaska’s Complex

    B. Pigulski, A. Jarszak and S. Szafert, Dalton Trans., 2018, Accepted Manuscript , DOI: 10.1039/C8DT04219E

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