Ferrocene crystal structure

Keywords polysilanes, ferrocene, crystal structure, Mossbauer spectroscopy... 

Takusagawa F, Koetzle TF (1979) A neutron diffraction study of the crystal structure of ferrocene. Acta Crystallogr B 35 1074-1081... 

The 1,4,7-trithiacyclononane ligand, [9]aneS3, zinc complex was synthesized to compare with the electrochemistry of related complexes and showed an irreversible oxidation and an irreversible reduction at +1.30 V and —1.77 V vs. ferrocene/ferrocenium, and the X-ray crystal structure of the bis macrocycle zinc complex was reported.5 0,720... 

Elimination of hydrogen halides from dihalogenoorganylboranes by reaction with ferrocene-1,1 -dithiol resulted in l,3-dithia-2-boryl[3]ferrocenophanes.170 These borylferrocenophanes were air sensitive, but were characterized by NMR, MS, and elemental analysis.170 A series of l,3-dibora-2-X-[3]fer-rocenophanes (X=S, Se, Te) were prepared and characterized and the crystal structure of [Se N Pr2)BC5Fl4 2Fe] has been reported.171... 

Over the past decade a number of new covalently bonded TTF/ferrocene adducts have been reported [77, 78]. The crystal structure of the l,l -bis(l,3-dithiole-2-ylidine)-substituted ferrocene derivative has been published [77]. In this complex, ferrocene has essentially been incorporated as a molecular spacer between the two l,3-dithole-2-ylidene rings forming a stretched TTF molecule. This adduct, and its methyl-substituted derivative, have been combined with TCNQ to form charge-transfer complexes with room temperature powder conductivities of 0.2 S cm-1. Similar diferrocenyl complexes have been prepared with bis (dithiolene) metal complexes [79, 80]. 

One example of a cocrystal containing BEDT-TTF and ferrocene has been reported [104]. The [(BEDT-TTF Cgob lferrocene) adduct was crystallized from a carbon disulfide solution. The unit cell has been determined by single crystal X-ray diffraction but the crystal structure was not reported. An infrared spectroscopic analysis indicates that the charge transfer between the BEDT-TTF and C6o molecules is quite small. It has been suggested that such complexes may offer a means to introduce iron into the fullerene lattice. 

C4H6)Fe(CO)3. The elucidation of the structure of ferrocene eventually lead Hallam and Pauson2 to propose a jr-complex (1) for (C4H6)Fe(CO)3 and this was eventually confirmed by crystal structure analysis at low temperature3. Since that time interest in... 

Since the discovery of ferrocene and the development of metallocene chemistry, the compound cyclopentadienyllithium, C5H5Li, has been of considerable interest to both experimentalists and theoreticians. In its physical properties cyclopentadienyllithium qualitatively behaves like a typical salt. It is nearly insoluble in noncoordinating solvents and possesses a high melting (decomposition) point and a very low volatility. To our knowledge the crystal structure of C5H5Li is unknown. 

In terms of basicity, pA s of the two drugs indicate that FQ is less basic than CQ (Table 1, [129]). Crystal structure of FQ (Fig. 23) shows the presence of a strong internal hydrogen bond between the anilino (Nil) group and the tertiary amino N(24) [128]. This, together with the electron donating properties of the ferrocene moiety, should explain the decreased pKa values. 

Upon treatment with an ethereal solution of methyllithium, both oligocydopropyl-substituted cyclopentadienes 14 and 6 in tetrahydrofuran were quantitatively deprotonated to the corresponding cyclopentadienides 14-Li and 6-Li, respectively, which were characterized by their 1H and 13 C NMR spectra. Treatment of the solutions of 14-Li and 6-Li with solutions of iron(II) chloride in tetrahydrofuran yielded the l,l, 2,2, 3,3, 4,4 -octacydopropylferrocene (16) (74%) and the decacyclopropylferrocene (17) (21%). After crystallization from hexane (for 16) and pentane/dichloromethane (for 17), the structures of both ferrocenes were established by X-ray crystal structure analyses (Scheme 3). The electron-donating effect of the cyclopropyl substituents on these cyclopentadiene systems is manifested in the oxidation potentials of the ferrocenes 16 and 17. While the parent ferrocene has an oxidation potential E1/2 (vs. SCE) = +0.475 V, that of decamethylferrocene is significantly lower with Ei/2 = —0.07 V, and so are those of 16 (Ey2 — —0.01 V) and 17 (f i/2 = —0.13 V) [13]. 

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