Ferrocene inclusion compound

Metallocenes (but only with unsubstituted cyclopentadienyl rings) also form thiourea inclusion compounds. X-ray diffraction and Mdssbauer data on the ferrocene inclusion compound show that at 295 K the guest molecules are orientationally disordered at the sites of 32 symmetry. A phase change at 162 K generates a more ordered structure78). 

The crystal structure of the a-CD/ferrocene inclusion compound has been determined by an X-ray analysis which shows that the ferrocene molecule is encapsulated by the dimer of the a-CD in a tail-to-tail orientation and inclined... 

Clement R. Gourdji. M. Guibe, L. Molecular motions in the thiourea-r/4-ferrocene inclusion compound. Chem. Phys. Lett. 1980. 72. 466. 

Heyes, S.J. Clayden, N.J. Dobson, C.M. Ferrocene molecular reorientation in the (thioureajs ferrocene inclusion compound as studied by deuteron NMR spectroscopy. J. Phys. Chem. 1991 95. 1547. 

Cyclodextrin Inclusion Compounds of Organometallic Complexes. Ferrocene Inclusion Compounds... 

PREPARATION AND PROPERTIES OF CYCLODEXTRIN INCLUSION COMPOUNDS OF ORGANOMETALLIC COMPLEXES. FERROCENE INCLUSION COMPOUNDS... 

Ferrocene We have recently found that DCA forms inclusion compounds with ferrocene and its derivatives. Particularly DCA-ferrocene inclusion compound is very easy to get a large crystal enough to analyze the crystal structure by X-ray diffraction method. It was found from the analysis of a single crystal that ferrocene molecules are tightly accommodated into a DCA canal in an array different from those of crystals of ferrocene itself [18]. It was also ascertained that DCA-ferrocene inclusion compounds are doped with iodine. On the other hand, apoCA does not form an inclusion compound with ferrocene itself, but with its derivatives. 

CA 72, 113395 (1970) claims thermites and thermates (thermites + flake Al, S, hydrocarbon oil and/or oxidizers such as Ba(N03)2, KMu04, etc) of improved ignitability due to inclusion of 2-50% of ferrocene-type compounds. 

Odagaki, Y., Hirotsu, K., Higuchi, T., Harada, A., Takahashi, S., X-ray structure of the alpha-cyclodextrin ferrocene (2-1) inclusion compound. J. Chem. Soc.-Perkin Trans. 1 1990, 1230-1231. 

Chlathrates may, in a way, be regarded as supramolecular adducts in the crystalline state. C ) forms a series of these compounds which in most cases are obtained by simple cocrystallization of their constituents. Known examples are the inclusion compounds with hydrocarbons tike pentane or nonane, etc., but chlathrates of Qo or C70 have also been found with hydroquinone in the presence of benzene. In these cases the fullerene molecules occupy interstitial spaces within the crystal structure of hydroquinone and form donor-acceptor complexes. Further inclusion compounds with fuUerenes are known for ferrocene and other inorganic substances such as sulfur (Sg), white phosphorus (P4) or complexes hke (PhCN)2PdCl2 and PhsPAuCl (also refer to Section 2.5.3). For the complex of > with ferrocene the crystal structure of the first is found with the latter inserted into the given gaps. The whole stracture can only exist because ferrocene is too weak a reducing agent to transform > into Qo. 

Thiourea forms a layered lattice able to act as host for some organometallic guest molecules. The ferrocene-thiourea inclusion compound has been investigated by spectroscopic methods (NMR, Mossbauer) and it has been shown that the thiourea host structure is preserved [492-502]. Other inclusion compounds of thiourea with organometallics such as ( /" -l,3-cyclohexadiene)Mn(CO)3, (7/ -C6H6)Cr(CO)3, (/ -l,3-cyclohexadiene)Fe(CO)3, and t/ -C(CH2)3Fe(CO)3 have been reported [503, 504]. 

The CD -ferrocene complexes were characterized by elemental analysis, IR, UV, and H-NMR spectra. Stoichiometries were determined by elemental analysis, and especially the iron content measured by atomic absorption analysis and from the H-NMR spectra, which show all the complexes obtained here are stoichiometric compounds and have definite ratios of CD/guest depending on the combinations of host and guest. Table I shows the results of the preparation of inclusion compounds of CDs with ferrocene. 3 CD formed 1 1 inclusion compounds with ferrocene. 

NMR also has been used to further elucidate the structure and dynamic state of the ferrocene-thiourea inclusion compound [21,22] previously studied by Mossbauer techniques [23], [24] and C [25] NMR. First of all, a new single crystal Mossbauer... 

Besides Scheme 3.45, one more case of ferrocenylammoninm oxidation deserves to be considered. That is, the chemical oxidation of the confined species. fV-(ferrocenylmethylene)-A/,A/,Af-trimethylam-monium forms a remarkably stable inclnsion complex with cucurbituril (Jeon et al. 2005). Yuan and Macartney (2007) used aqueous solution of the bis(2,6-pyridinedicarboxylato)cobaltate(III) ion for comparative oxidation of free and included compounds. This oxidant does not bind to curcubituril. As it turned out, the inclusion significantly reduces the rate constants for the ferrocenyl-ferroceniumly transition. One of the important causes of the retardation observed is the steric hindrance due to close approach of the oxidant to the encapsulated ferrocene (Yuan and Macartney 2007). 

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