Reactions of arylpalladium complexes with ammonia and chelating amines. Crystal and molecular structure of [Pd(o-C6H4CHNCH2CH2NH2)(NH2CH2CH2NH2)][PF6], a product of transamination and ligand substitution
Abstract
Reaction of trans-[Pd(Ph)(PPh3)2Cl] with NH3, NH2CH2CH2NH2(en), and NH2(CH2)3NH2(pn) afforded trans-[Pd(Ph)(PPh3)2(NH3)]+ and [Pd(Ph)(PPh3)(N–N)]+ where N–N = en or pn. Treatment of [{Pd(o-C6H4CHNPh)X}2](X = Cl or O2CMe) with ammonia gave [Pd(o-C6H4CHNPh)(NH3)X], but with an excess of NH3, [Pd(o-C6H4CHNPh)(NH3)2]Cl and [Pd(o-C6H4CHNPh)(NH3)3][O2CMe] were formed. With 1,2-bis-(dimethylamino)ethane, [Pd(o-C6H4CHNPh)(Me2NCH2CH2NMe2)]+ was isolated whereas with en, a transamination reaction occurred giving [Pd(o-C6H4CHNCH2CH2NH2)(en)]+. The structure of this cation (as the PF6– salt) was determined crystallographically. Crystals are triclinic, space group P, a= 8.109(16), b= 11.027(27), c= 18.93(4)Å, α= 88.30(19), β= 83.19(18). γ= 81.05(18)°, and Z= 4. The NH2 group of the o-C6H4CHNCH2CH2NH2 ligand is not co-ordinated to palladium.