Some reactions of nitrosyl complexes of nickel, palladium, and platinum

Abstract

The reactions of [Ni(NO₂)XL₂][X = Cl, L =½ dppe (dppe = Ph₂PCH₂CH₂PPh₂), PPh₃, PPrⁿ₃, OPPh₃, or NC₅H₅; X = Br, L =½ dppe or PPh₃; X = NO₂, L =½ dppe] and trans-[M(NO₂)₂L₂](M = Pd, L = PEt₂Ph or PEt₃; M = Pt, L = PEt₂Ph, PEt₃, or PBuⁿ₃) with carbon monoxide have been examined. The nickel compounds react to produce the corresponding nitrosyl compounds [Ni(NO)XL₂] and CO₂. The palladium and platinum compounds react with CO to form [M(CO)₂L₂] complexes and subsequently higher clusters, except for [Pt(NO₂)₂(PEt₃)₂] where evidence for the formation of [Pt(NO)(NO₂)(PEt₃)₂] and [Pt(NCO)(NO₂)(PEt₃)₂] has been found. On reaction with dioxygen the compounds [Ni(NO)XL₂] afford the nitro-complexes [Ni(NO₂)XL₂] exclusively, the rate of the reaction depending on L. The compound [Pt(NO)(NO₃)(PPh₃)₂], prepared from the reaction of N₂O₄ with [Pt(PPh₃)₄] in toluene, reacts with O₂ to produce trans-[Pt(NO₃)₂(PPh₃)₂]. In solution, [Pt(NO)(NO₃)(PPh₃)₂] undergoes an intramolecular reaction to form [Pt(NO₂)₂(PPh₃)₂]. The complex [Pt(N₂O₂)(PPh₃)₂] reacts with [NO][PF₆] to form [{Pt(PPh₃)₂}₂N₂O₂][PF₆]₂.