Synthesis Of New Cyclopentadienyl-, Indenyl- And Fluorenylphosphanes By The Reaction Of Carbanions Of The Cyclopentadienyl Type With Alkyl(Aryl)Chloro-N,N-Dialkylaminophosphanes

Keywords: Titanium / Zirconium / Cyclopentadienyl ligands / P ligands / PolymerisationPhosphanyl-substituted cyclopentadienes of the type [R n Cp−PR(NR 1 R 2 /Cl)] (1−22) (R = Alk, Ar; R 1 , R 2 = H, Alk, Ar, SiR 3 ; R n Cp = tBuCp, Me 4 Cp, Ind, Me 6 Ind, Flu) can be synthesised by reaction of alkyldichlorophosphanes and alkyl(amino)chlorophosphanes with alkali metal cyclopentadienides. The method used is a general one and provides high isolated yields of the target compounds. The phosphanylcyclopentadienes can easily be deprotonated by strong bases (e.g. nBuLi, PhCH 2 K, Ph 2 CHK) and the potassium salts [R n Cp−PR(NR 1 R 2 )]K (25−28) are efficiently transmetallated by Me 3 SnCl. A subsequent reaction with TiCl 4 (L) 2 and ZrCl 4 (L) 2 (L = THF, tetrahydrothiophene, Me 3 P) affords new half-sandwich complexes [{Me 4 Cp−PtBu(NEt 2 )}TiCl 3 ] (36), [{Me 4 Cp−PtBu(NEt 2 )}TiCl 3 ] (37) and [{tBuCp−PtBu-(NEt 2 )}TiCl 3 ] (38) in moderate yields. The reaction of [tBuCp−PtBu(Cl)] (6) with TiCl 4 in the presence of Et 3 N at low temperature yields the half-sandwich complex

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Alkyl(amino)- and Alkyl(chloro)phosphanyl-Substituted Cyclopentadienyl Complexes of Titanium and Zirconium

Котов

Avtomonov

Harms

et al. 2002

Eur. J. Inorg. Chem.

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Alkylaminophosphanyl substituted half-sandwich complexes of vanadium(III) and chromium(III): preparation and reactivity in ethylene polymerisation

Котов

Avtomonov

Aitola

et al. 2001

Journal of Organometallic Chemistry

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

et al. 2017

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This paper focuses on ferrocene-based secondary diphosphines of the type [Fe{η-CH(PHR)}] 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{η-CH(PHPh)}] (H1a) and [Fe{η-CH(PHt-Bu)}] (H1b) with n-BuLi in the presence of TMEDA afforded lithium diphosphides of the type [Li(μ-1)(TMEDA)], which contain a cyclic non-planar LiP core. The analogous reactions of [Fe{η-CH(PHMe)}] (H1c) and [Fe{η-CH(PHNp)}] (H1d) furnished dimeric aggregates exhibiting a ladder-type LiP motif, viz. [Li(μ-1c)(TMEDA)] and [Li(μ-1d)(TMEDA)]. H1e (R = XyF) did not afford a stable lithium diphosphide. A Brønsted metathesis with Zr(NMe) was possible with the aryl-substituted compounds H1a and H1e, leading to products of the type [{Zr(NMe)}(μ-1)]. In contrast, the alkyl-substituted congeners H1b-H1d were inert towards Zr(NMe). The reaction of [Fe{η-CH(PHR)}] with nickelocene afforded intractable mixtures of numerous products in the case of H1c and H1e. In the other three cases, compounds of the type [(NiCp)(μ-1)] were isolated. For H1b and H1d 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)].

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Synthesis Of New Cyclopentadienyl-, Indenyl- And Fluorenylphosphanes By The Reaction Of Carbanions Of The Cyclopentadienyl Type With Alkyl(Aryl)Chloro-N,N-Dialkylaminophosphanes

Cited by 3 publications

References 2 publications

Alkyl(amino)- and Alkyl(chloro)phosphanyl-Substituted Cyclopentadienyl Complexes of Titanium and Zirconium

Alkyl(amino)- and Alkyl(chloro)phosphanyl-Substituted Cyclopentadienyl Complexes of Titanium and Zirconium

Alkylaminophosphanyl substituted half-sandwich complexes of vanadium(III) and chromium(III): preparation and reactivity in ethylene polymerisation

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

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