Phosphido complexes derived from 1,1'-ferrocenediyl-bridged secondary diphosphines

This paper focuses on ferrocene-based secondary diphosphines of the type [Fe{η⁵-C₅H₄(PHR)}₂] with P-substituents of distinctly different steric and electronic properties, namely methyl, neopentyl (Np), tert-butyl, phenyl and 3,5-bis(trifluoromethyl)phenyl (XyF). The reaction of [Fe{η⁵-C₅H₄(PHPh)}₂] (H₂1a) and [Fe{η⁵-C₅H₄(PHt-Bu)}₂] (H₂1b) with n-BuLi in the presence of TMEDA afforded lithium diphosphides of the type [Li₂(μ-1)(TMEDA)₂], which contain a cyclic non-planar Li₂P₂ core. The analogous reactions of [Fe{η⁵-C₅H₄(PHMe)}₂] (H₂1c) and [Fe{η⁵-C₅H₄(PHNp)}₂] (H₂1d) furnished dimeric aggregates exhibiting a ladder-type Li₄P₄ motif, viz. [Li₄(μ-1c)₂(TMEDA)₃] and [Li₂(μ-1d)(TMEDA)]₂. H₂1e (R = XyF) did not afford a stable lithium diphosphide. A Brønsted metathesis with Zr(NMe₂)₄ was possible with the aryl-substituted compounds H₂1a and H₂1e, leading to products of the type [{Zr(NMe₂)₃}₂(μ-1)]. In contrast, the alkyl-substituted congeners H₂1b-H₂1d were inert towards Zr(NMe₂)₄. The reaction of [Fe{η⁵-C₅H₄(PHR)}₂] with nickelocene afforded intractable mixtures of numerous products in the case of H₂1c and H₂1e. In the other three cases, compounds of the type [(NiCp)₂(μ-1)] were isolated. For H₂1b and H₂1d a two-stepped reaction via a phosphino-phosphido intermediate of the type [NiCp(H1)] was observed, which could be isolated and fully characterised in the case of [NiCp(H1b)].