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Issue 43, 2010
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Alkyne insertion into cyclometallated pyrazole and imine complexes of iridium, rhodium and ruthenium; relevance to catalytic formation of carbo- and heterocycles

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Abstract

The cyclometallated complexes [MCl(C⁁N)(ring)] (HC⁁N = 2-phenylpyrazole, M = Ir, Rh ring = Cp*; M = Ru, ring = p-cymene) readily undergo insertion reactions with RC[triple bond, length as m-dash]CR (R = CO2Me, Ph) to give mono insertion products, the rhodium complex also reacts with PhC[triple bond, length as m-dash]CH regiospecifically to give an analogous product. The products of the reactions of the cyclometallated imine complexes [MCl(C^N)Cp*] (HC⁁N = PhCH[double bond, length as m-dash]NR, R = Ph, CH2CH2OMe, Me; M = Ir, Rh) with PhC[triple bond, length as m-dash]CPh depend on the substituent R; when R = CH2CH2OMe a monoinsertion is observed, however for R = Me the initial insertion product is unstable, undergoing reductive elimination with loss of the organic fragment, and for R = Ph no metal-containing product is isolated. With PhC[triple bond, length as m-dash]CH the cyclometallated imine complexes can give mono or di-insertion products. The implications for catalytic synthesis of carbo- and heterocycles by a tandem C–H activation, alkyne insertion mechanism are discussed.

Graphical abstract: Alkyne insertion into cyclometallated pyrazole and imine complexes of iridium, rhodium and ruthenium; relevance to catalytic formation of carbo- and heterocycles

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Publication details

The article was received on 09 Apr 2010, accepted on 25 May 2010 and first published on 06 Oct 2010


Article type: Paper
DOI: 10.1039/C0DT00280A
Citation: Dalton Trans., 2010,39, 10447-10457
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    Alkyne insertion into cyclometallated pyrazole and imine complexes of iridium, rhodium and ruthenium; relevance to catalytic formation of carbo- and heterocycles

    Y. Boutadla, D. L. Davies, O. Al-Duaij, J. Fawcett, R. C. Jones and K. Singh, Dalton Trans., 2010, 39, 10447
    DOI: 10.1039/C0DT00280A

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