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

作者：Boutadla Youcef; Davies David L^*; Al Duaij Omar; Fawcett John; Jones Rachel C; Singh Kuldip

来源：Dalton Transactions, 2010, 39(43): 10447-10457.

DOI：10.1039/c0dt00280a

The cyclometallated complexes [MCl((CN)-N-boolean AND)(ring)] ((HCN)-N-boolean AND = 2-phenylpyrazole, M = Ir, Rh ring = Cp*; M = Ru, ring = p-cymene) readily undergo insertion reactions with RC CR (R = CO2Me, 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((CN)-N-boolean AND) Cp*] ((HCN)-N-boolean AND = PhCH=NR, R = Ph, CH2CH2OMe, Me; M = Ir, Rh) with PhC 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 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.

• 出版日期2010