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|Title:||Alkyne insertion into cyclometallated pyrazole and imine complexes of iridium, rhodium and ruthenium; relevance to catalytic formation of carbo- and heterocycles.|
|Citation:||DALTON TRANS, 2010, 39 (43), pp. 10447-10457|
|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≡CR (R = CO(2)Me, Ph) to give mono insertion products, the rhodium complex also reacts with PhC≡CH regiospecifically to give an analogous product. The products of the reactions of the cyclometallated imine complexes [MCl(C^N)Cp*] (HC^N = PhCH=NR, R = Ph, CH(2)CH(2)OMe, Me; M = Ir, Rh) with PhC≡CPh depend on the substituent R; when R = CH(2)CH(2)OMe 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≡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.|
|Appears in Collections:||Published Articles, Dept. of Chemistry|
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