Structure of Stable Telluradiphosphirane Bearing Bulky Ferrocenyl Ligands

Abstract

Chalcogenation reactions of 1,2-bis(ferrocenyl)diphosphene, Fc*P=PFc* (Fc*: 2,5-bis(3,5-di-t-butylphenyl)ferrocenyl), with elemental sulfur (S8) and tellurium afforded the corresponding thia- and telluradiphosphirane derivatives as stable crystalline compounds, respectively. The sterically demanding ferrocenyl group would afford sufficient crystallinity and stability to the heterocyclic compounds; the structures of these three-membered ring heterocycles were revealed by X-ray crystallographic analysis.

Isolation and Ambident Reactivity of a Chlorogermylenoid

“…Initially, we prepared the sterically demanding ferrocenyl bromide Fc*Br and (Fc*Li) 2 ( 1 ) according to previously reported procedures . Subsequently, 1 was treated with an equimolar amount of GeCl 2 ⋅dioxane in toluene at room temperature to afford an orange powder (Scheme ).…”

“…[11] Initially,w ep repared the sterically demanding ferrocenyl bromide Fc*Br and (Fc*Li) 2 (1)a ccording to previously reported procedures. [12,13] Subsequently, 1 was treated with an equimolar amounto fG eCl 2 ·dioxane in toluenea tr oom temperature to afford an orange powder (Scheme 1). The 1 HNMR spectrum of a[ D 8 ]THF solutiono ft his powder exclusively exhibited the signals associated with the Fc* moiety,w hichs uggests the formationo f2 as the sole product (quantitative by 1 HNMR analysis).…”

The Synthesis and Properties of Bimetallic d-^|^pi; Electron Systems Containing Metallocenyl Substituents of Fe or Ru, and ^|^pi;-Electron Spacers of Heavier Main Group Elements from Group 14 or 15

“…Therefore, we developed an alternative synthetic route for these haloferrocenes: Lithiation of bromoferrocene with LiTMP (TMP 2,2,6,6 tetramethylpiperidide) resulted in the formation of 1,2 bromolithioferrocene, which was subjected to a Negishi cross coupling reaction with ArX (DmpI or DtpBr), affording the 1 bromo 2 Ar ferrocenes (29). 34 The introduction of another Ar group was achieved by subjecting 29 to a second Negishi cross coupling reaction to give the corresponding 1 bromo 2,5 Ar 2 ferrocenes (30). The generation of Fc Li and Fc Li by treatment of 30a and 30b with n BuLi was proven by the subsequent addition of water,…”

Generation of Bis(ferrocenyl)silylenes from Siliranes

“…In order to find the right balance in this trade-off relationship, transient silylenes with a combination of very bulky and less hindered groups have been designed. Our group has already reported the design and synthetic utility of the sterically demanding 2,5-bis(3,5-di- t -butylphenyl)-1-ferrocenyl (Fc*) group [ 40 , 41 , 42 ], and this group should be an appropriate substituent for bis(ferrocenyl)silylene 1 ( Chart 1 ), which bears Fc* and ferrocenyl (Fc) groups on the silicon center [ 43 ]. Silylene 1 can be expected to (i) be very reactive due to its low-lying LUMO level, and (ii) show intriguing redox activity on account of its two ferrocenyl moieties.…”