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Heterobimetallic Iron-Rhodium Complexes. Synthesis and Characteristics of CpFe(mu-eta5:eta5-as-indacenediide)RhL2 (L2 = COD, NBD, (ethylene)2) (Articolo in rivista)

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Heterobimetallic Iron-Rhodium Complexes. Synthesis and Characteristics of CpFe(mu-eta5:eta5-as-indacenediide)RhL2 (L2 = COD, NBD, (ethylene)2) (Articolo in rivista) (literal)

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Santi C., Ceccon A., Carli F., Crociani L., Bisello A,, Tiso M., Venzo A. (2002)
Heterobimetallic Iron-Rhodium Complexes. Synthesis and Characteristics of CpFe(mu-eta5:eta5-as-indacenediide)RhL2 (L2 = COD, NBD, (ethylene)2)
in Organometallics
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Santi C., Ceccon A., Carli F., Crociani L., Bisello A,, Tiso M., Venzo A. (literal)

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New synthetic strategies for the achievement of the instrumental goals have been developed; in particular, we improved a synthetic pathway recently suggested by Chung et al. and consisting of the use of [CpFe(eta6-fluorene)]PF6 as an FeCp transfer reagent. Thus, the lithium salt of s- (or as-) hydroindacenide was reacted with CpFe(eta5-fluorenide) to obtain the complexes Cyclopentadienyliron(eta5-hydro-s-indacenide) (s-1) and Cyclopentadienyliron(eta5-hydro-as-indacenide) (as-1) in 55-65% yield (by NMR integration of the crude mixture). Purification by column chromatography on silica or alumina gave different results for the two complexes. In fact, we have been able to obtain pure as-1 (as a 2/3 mixture of the 1-hydro- and 3-hydro isomers) in good yield (ca. 58%) with little decomposition. On the contrary, s-1 was obtained pure in a very small amount owing to its high instability under the chromatographic conditions. (literal)

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The cooperative effect of two transition metals linked to the same poli-site organic ligand is studied by X-Ray diffraction, NMR spectroscopy and electrochemical techniques (literal)

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Heterobimetallic compounds in which two metal atoms have the potential to interact with each other by direct means or through a suitable bridging ligand have been the target of many research groups. Thus, the characteristic properties of one metal may be changed substantially by the presence of the other metal center. Moreover, the effects can be modulated by changing the oxidation state of one of the two partners. In this respect the ferrocenyl group, Fc, an easily oxidable moiety, has been frequently coupled with metals such as chromium, molybdenum, tungsten, and manganese. In these complexes two cyclopentadienyl rings (or one Cp ring and one benzene ring) are directly linked through a sigma bond or connected by a saturated or unsaturated hydrocarbon chain. In indacenyl complexes the two metals would instead participate with the whole 14-pi-electron system of the bridge, so that the coordination mode of one metal is expected to influence the coordination of the second. The particular physical and chemical characteristics of the second metal would also be influenced to a great extent. (literal)

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Titolo

Heterobimetallic Iron-Rhodium Complexes. Synthesis and Characteristics of CpFe(mu-eta5:eta5-as-indacenediide)RhL2 (L2 = COD, NBD, (ethylene)2) (literal)

Abstract

The heterobimetallic CpFe(eta5:eta5-as-indacenediide)RhL2 complexes (L2 = COD (2), NBD (3), (ethylene)2 (4)) have been obtained from metalation of the mononuclear lithium CpFe-(eta5-as-indacenediide) with [Rh(mu-Cl)L2]2. Mixtures of syn and anti heterobimetallic complexes were formed and fully characterized by 2D NMR spectroscopy. The reactivity at the rhodium center is greatly influenced by the presence of the ferrocenyl moiety. The voltammetric behavior and the optical spectra are in favor of the existence of significant electronic interactions between the two metals. (literal)

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