Reactions of phosphine, arsine, and stibine with carbonylbis(triethylphosphine)iridium(I) halides. Part 1. Reactions in toluene; X-ray crystal structures of [Ir(CO)ClH(PEt3)2(AsH2)] and [Ir(CO)XH(PEt3)2(µ-ZH2)RuCl2(η6-MeC6H4CHMe2-p)](X = Br, Z = P; X = Cl, Z = As)

Abstract

trans-[Ir(CO)X(PEt₃)₂](X = Br or Cl) reacts with ZH₃(Z = P, As, or Sb) in toluene at 180 K to give [Ir(CO)XH(PEt₃)₂(ZH₂)]. When Z = P or As, the product is monoisomeric, but with Z = Sb two isomers are formed. [Ir(CO)BrH(PEt₃)₂(P′H₂)](4) reacts with Cl₂ to give [Ir(CO)BrClH (PEt₃)₂]; with Se, [Ir(CO)BrH(PEt₃)₂(P′H₂Se)] is the product. Reaction with HCl at 200 K gives [Ir(CO)BrH(PEt₃)₂(P′H₃)]⁺, but as the solution is allowed to warm PH₃ is displaced by Cl, and a similar reaction with H₂Se leads to the formation of [Ir(CO)BrH(PEt₃)₂(SeH)]. Boron trifluoride does not interact with (4), but B₂H₆ reacts to give a BH₃ adduct that is stable in solution at room temperature. Compound (4) reacts with [{RuCl₂(η⁶-MeC₆H₄CHMe₂-p)}₂], forming [Ir(CO)BrH(PEt₃)₂(µ-P′H₂)RuCl₂(η⁶-MeC₆H₄CHMe₂-p)]. Reactions of [Ir(CO)ClH(PEt₃)₂(AsH₂)](5) are similar, except that treatment with Se leads to decomposition. The crystal structures of (5) and the complexes formed by both (4) and (5) with [{RuCl₂(η⁶-MeC₆H₄CHMe₂-p)}₂] are reported.