Reactions involving transition metals. Part 18. Reactions of transition-metal complexes with peroxycarboxylic acids, diacyl peroxides, and t-butyl peroxybenzoate
Abstract
The iridium(I) complexes [IrX(L1)(L2)2](L1= CO or N2) react with peroxycarboxylic acids, RCO3H, to give the carboxylato-complexes [IrX(O2CR)2(L2)2](X = Cl, R = 3-ClC6H4, L2= PPh3, PPh2Me, or AsPh3; X = Cl, R = Ph, L2= PPh3 or AsPh3; X = Cl, R = Me, L2= PPh3; X = Br, R = 3-ClC6H4, L2= PPh3) with evolution of carbon dioxide; the compounds (X = Cl, L2= PPh3, R = Me, Ph, or 3-ClC6H4) have also been obtained from [IrCl(N2)(PPh3)2] and diacyl peroxides. The iodo-complex [Irl(CO)(PPh3)2] behaves anomalously giving [Ir(O2CR)3(PPh3)2] with RCO3H (R = Ph or 3-ClC6H4), and a mixture of [Ir(O2CPh)3(CO)(PPh3)2] and [Irl3(CO)(PPh3)2] with dibenzoyl peroxide. Diacyl peroxides, (RCO2)2, react with [IrCl(CO)(PPh3)2] to give the complexes [IrCl(O2CR)2(CO)(PPh3)2](R = Ph or 3-ClC6H4) in high yields, and the compound where R = Ph rather than the expected [IrCl(O2CPh)(O2CMe)(CO)(PPh3)2] is formed under similar conditions with acetyl peroxybenzoate. The palladium(0) complexes [PdL4](L = PPh3 or ½Ph2PCH2CH2PPh2) react to form [Pd(O2CPh)2L2] with dibenzoyl peroxide at room temperature, but [M{P(OEt)3}4](M = Pt or Pd) and [Pd2(PhCH![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
CHCOCHCHPh)3] do not react under these conditions. Similarly, there is no reaction between [IrCl-(CO)(PPh3)2] and the peroxy-ester ButO2C(O)Ph at room temperature, but [Pt(PPh3)4] and [Pd(Ph2PCH2CH2PPh2)2] give [Pt(O2CPh)2(PPh3)2] and [Pd(O2CPh)2(Ph2PCH2CH2PPh2)] respectively as the only metal-containing products.
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