Wydział Chemii

Bartłomiej Pigulski

Agata Jarszak

Sławomir Szafert

2018

Dalton Transactions

47

17046-17054

10.1039/c8dt04219e

Naukowa

Angielski

Artykuł

The reaction of bis(triphenylphosphine)iridium(I) carbonyl chloride (Vaska's complex) with a series of 1-iodopolyynes (1-C_nI and 2-C_nI) gave σ-polyynyl iridium(III) complexes with general formula R(CC)_nIr(PPh₃)₂(Cl)(I)(CO). The use of acetonitrile as a solvent appeared crucial and allowed selectively obtaining only one from a few possible isomers. The X-ray single crystal diffraction experiment for 2-C₄[Ir]I allowed the determination of the exact structure of this complex. Further spectroscopic measurements, especially ³¹P NMR, confirmed the 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 a linear carbon chain from butadiyne to decapentayne are the longest iridium end-capped polyynes known to date since only compounds with a (CC)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.

http://dx.doi.org/10.1039/c8dt04219e

https://www.rsc.org/