Synthesis and coordination of hybrid phosphinoferrocenes with extended donor pendants

Combining a phosphinoferrocene fragment with extended multidonor moieties affords novel, flexible multidonor pro-ligands. This contribution describes the synthesis of two structurally similar functional phosphines, Ph₂PfcNHC(O)CH₂PPh₂ (1) and Ph₂PfcNHCH₂CH₂PPh₂ (2, fc = ferrocene-1,1'-diyl), and their coordination behaviour towards Pd(II). The former amidophosphine reacts with [PdCl₂(MeCN)₂] to produce the chelate complex [PdCl₂(1-κ²P,P')] as a mixture of cis and trans isomers, which convert into bis-chelate [PdCl₂(Ph₂PfcNC(O)CH₂PPh₂-κ³P,P',N)] upon reacting with a strong base (KOt-Bu). In contrast, the more flexible and more basic phosphinoamine 2 directly forms the cationic bis-chelate complex [PdCl(2-κ³P,P',N)]Cl via spontaneous self-ionisation. Subsequent halogen abstraction with Ag[SbF₆] results either in counter ion exchange to give [PdCl(2-κ³P,P',N)][SbF₆] or in the formation of a structurally unique complex [PdCl(2-κ⁴Fe,P,P',N)][SbF₆]₂ with an Fe → Pd dative interaction, depending on the amount of silver(I) salt used (1 or 2 equiv.).