Metallorganische verbindungen des iridiums und rhodiums: XXVI. CH-metallierung und hydridbildung im system Ir2Cl2(C8H14)4/PR3(PR3 = P(CH2CMe3)3, t-BuP(CH2CMe3)2, t-Bu2PCH2CMe3; i-Pr3P

Treatment of Ir₂Cl₂(C₈H₁₄)₄ with the phosphines t-Bu_3?nP(CH₂CMe₃)_n (n = 3,2,1) in hot toluene followed by crystallization of the products from C₇H₈/ EtOH mixtures gave the cyclometallated hydrides (C₈H₁₄)₂Ir-μ-Cl₂$\text{IrHCH}{}_2\text{CMe}{}_2\text{CH}{}_2\text{P}$(CH₂CMe₃)₂]P(CH₂ (I) t-BuP(CH₂CMe₃)₂]₂H₂Ir-μ-Cl₂$\text{IrHCH}{}_2\text{CMe}{}_2\text{CH}{}_2\text{P}$Bu^t(CH₂CMe₃)]t-BuP(CH₂CMe₃)₂] (II), and (t-Bu₂$\text{PCH}{}_2\text{CMe}{}_2\text{CH}{}_2\text{)HI}$rCl]₂ (III). The dihydrides IrH₂Clt-BuP(CH₂CMe₃)₂]₂ (IIa) and IrH₂Cl(t-Bu₂PCH₂CMe₃)₂ (IIIa) were also isolated; these species were, however, more conveniently obtained by bubbling hydrogen through the solution of Ir₂Cl₂ (C₈H₁₄)₄ and the respective phosphine in toluene. i-Pr₃ reacted with the olefiniridium(I) precursor in C₇H₈/EtOH to yield the carbonyl complexes (i-Pr₃P)₂H₂Ir-μ-Cl₂Ir(CO)(PPrⁱ₃)₂ (IV) and IrCl(CO)(PPⁱ₃)₂ (IVa), no cyclometallated product being detected. The stereochemistries of the complexes were deduced from IR, ¹H, ³¹P, and ¹³C NMR data. The crystal structures of IIIa and IVa were also determined.