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Amine-catalyzed substitution in CpFe(CO) 2 I by phosphine and bisphosphine ligands.

Aneta KosińskaDaria JamrozAgnieszka J Rybarczyk-PirekSławomir WojtulewskiMarcin PalusiakJanusz ZakrzewskiBogna Rudolf
Published in: Dalton transactions (Cambridge, England : 2003) (2024)
We have found that amines significantly accelerate iodide substitution in CpFe(CO) 2 I (1) (Cp = η 5 -cyclopentadienyl) with phosphines and allow the synthesis of new complexes that are not available through reactions carried out without an amine. The reaction of equimolar amounts of 1 and triphenylphosphine in toluene containing DIPA afforded [CpFe(CO) 2 PPh 3 ] + I - within 5 min at room temperature in 72% yield (90% after 24 h). DIPA and pyrrolidine gave the highest yields of the tested amines. We performed a similar reaction using model bisphosphines 1,3-bis(diphenylphosphino)ethane (dppe) and 1,1'-bis(diphenylphosphino)ferrocene (dppf). The products depended on the reagent ratio and bore the CpFe(CO) 2 moiety coordinated to one or two phosphine phosphorus atoms. Chelates [CpFe(CO)(dppe)] + I - (4) and [Cp 2 Fe 2 (CO) 4 (dppe)] 2+ 2I - (5) were formed in 72% and 98% yield, respectively. We also performed the DIPA-catalyzed reaction of 1 with triethyl phosphite and obtained the product of an Michaelis-Arbuzov-like rearrangement, CpFe(CO) 2 [P(O)(OCH 2 CH 3 ) 2 ] (11). All complexes were characterized with spectroscopic analysis by NMR, FT-IR, and ESI-MS, and by XRD for three complexes. To clarify the reaction mechanism, we performed theoretical calculations of the intermolecular interactions between 1 and amine molecules. We propose two possible reaction mechanisms to explain the formation of products.
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