Iridium-assisted CC bond cleavage of 1-alkyne by water: preparation of new alkyl derivatives

Gabriele Albertin; Stefano Antoniutti; Alessia Bacchi; Giancarlo Pelizzi; Francesca Piasente

doi:10.1039/B303635A

Iridium-assisted CC bond cleavage of 1-alkyne by water: preparation of new alkyl derivatives

Gabriele Albertin,*^a Stefano Antoniutti,^a Alessia Bacchi,^b Giancarlo Pelizzi^b and Francesca Piasente^a

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* Corresponding authors

^a Dipartimento di Chimica, Università Ca' Foscari di Venezia, Dorsoduro 2137, Italy

^b Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Università di Parma, Parco Area delle Scienze 17/A, Italy

Abstract

Alkyl complexes IrCl₂(η¹-CH₂Ar)(CO)(PPh₃)₂ (1) [Ar = Ph (a), p-tolyl (b)] were prepared by allowing the hydride mer- or fac-IrHCl₂(PPh₃)₃ to react with terminal alkynes ArC [triple bond, length as m-dash] CH in the presence of water. The complexes were characterized spectroscopically (IR and ¹H, ³¹P, ¹³C NMR) and by the X-ray crystal structure determination of 1b. The acyl complex IrCl₂{C(O)CH₂C(CH₃)₃}(PPh₃)₂ (2) was also prepared by reacting mer-IrHCl₂(PPh₃)₃ with tert-butylacetylene HC [triple bond, length as m-dash] CC(CH₃)₃ in the presence of H₂O. A reaction path for the hydration of terminal alkyne in the presence of the Ir(III) complex leading to the cleavage of the CC bond, with the formation of the complexes 1 or 2 is also proposed. Acetylide complexes IrHCl(CCAr)(PPh₃)₃ (3), IrHCl(C [triple bond, length as m-dash] CAr)(AsPh₃)₃ (4) [Ar = Ph (a), p-tolyl (b)] and IrHCl(CCPh){PPh(OEt)₂}(PPh₃)₂ (5) were prepared by reacting IrHCl₂L₃ (L = PPh₃, AsPh₃) or IrHCl₂{PPh(OEt)₂}(PPh₃)₂ with lithium acetylide. Protonation reaction with Brønsted acids of the acetylide 3 was also studied and led to unstable vinyl derivatives. The stable vinyl [IrCl{η²-CH [double bond, length as m-dash] C(H)COOMe}L₂]BPh₄ (6,7) [L = PPh₃ (6), AsPh₃ (7)] complexes, instead, were prepared by allowing IrHCl₂L₃ to react first with AgCF₃SO₃ and then with methyl propiolate.

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Publication details

The article was received on 01 Apr 2003, accepted on 23 May 2003 and first published on 18 Jun 2003

Article type: Paper

DOI: 10.1039/B303635A

Citation: Dalton Trans., 2003,0, 2881-2888

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Iridium-assisted CC bond cleavage of 1-alkyne by water: preparation of new alkyl derivatives

G. Albertin, S. Antoniutti, A. Bacchi, G. Pelizzi and F. Piasente, Dalton Trans., 2003, 0, 2881
DOI: 10.1039/B303635A
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Dalton Transactions

Iridium-assisted CC bond cleavage of 1-alkyne by water: preparation of new alkyl derivatives

Abstract

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Publication details

Iridium-assisted CC bond cleavage of 1-alkyne by water: preparation of new alkyl derivatives

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