Article Dans Une Revue Dalton Transactions Année : 2025

Ansa -effects in alkaline earth metal octaphenylmetallocenophanes and a derived ansa -ferrocene

Thomas Simler
Glen Deacon
Peter Junk

Résumé

The synthesis and structural characterisation of a series of alkaline earth ansa-octaphenylmetallocenes (Mg, Ca, Sr, Ba) bearing an ethylene bridge are described. The complexes [AE(C5Ph4CH2)2(thf)n] (AE = Mg (1), Ca (2) n = 1; AE = Sr (3), Ba (4), n = 2) were obtained through reductive dimerisation of 1,2,3,4-tetraphenylfulvene, facilitated by zero-valent metals and fully characterised by NMR spectroscopy. Singlecrystal XRD studies reveal distinct binding differences of the Cp ligands to Mg in complex 1 compared to the heavier analogues (η3 vs. η5). Complex 3 is the first structurally characterised ansa-metallocene complex of Sr. An ansa-effect was observed for the Ba complex 4 which showed good stability at room temperature in contrast to the previously described non-bridged analogue. Efficient transmetallation from the Ca ansa complex 2 to FeCl2 provided the new ansa-ferrocene complex [Fe(C5Ph4CH2)2] (5). Structural, spectroscopic and electrochemical properties of this bent ferrocenophane complex were compared to those of the known unbridged octaphenylferrocene.

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hal-05275441 , version 1 (23-09-2025)

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Angus Shephard, Amal Bouammali, Aymeric Delon, Zhifang Guo, Sylviane Chevreux, et al.. Ansa -effects in alkaline earth metal octaphenylmetallocenophanes and a derived ansa -ferrocene. Dalton Transactions, 2025, 54 (37), pp.13918-13928. ⟨10.1039/d5dt01881a⟩. ⟨hal-05275441⟩
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