Cyclopentadienyls unsolvated

A recent development in the low-valent lanthanide area is the synthesis and X-ray structural determination of the unsolvated complex (C5Me5)2Sm 121). This species is the first structurally characterized bis(cyclopentadienyl)lanthanide species which has no other ligands in the metal coordination sphere. As such, it is the closest lanthanide analogue of the bis(ring)metallocene sandwich compounds like ferrocene. Samarocene was obtained by desolvation of (C5Me5)2Sm(thf)2 under high vacuum and sublimation of the product [Eq. (58)]. The sublimed crystals have a bent... 

Whereas complexes of unsubstituted and substituted cyclopentadienyl ligands represent the vast majority of all published compounds in organolanthanide chemistry, examples of isolated and fully characterized (including X-ray structural analyses) compounds containing only cr-bonded alkyl and aryl ligands are still fairly rare. The first structurally characterized homoleptic lanthanide alkyls became available through the use of bulky mono-, bis-, and tris(trimethyl-silyl)-substituted methyl ligands. Simple unsolvated alkyls of the rare earth elements have not yet been synthesized. 

The unsolvated cyclopentadienyl derivatives h -CjHjBeX (X = Cl, Br, I) are prepared by redistribution of the binary compounds [see Eq. (a)] at 50°C in the absence of solvent and isolated and purified by volatilization in vacuo. Stirring Be(C5Hj-h ,h )2 in ether with anhydr FeBrj at — 78°C to RT for 2 h forms volatile h -CjHjBeBr which is separated by sublimation [RT 10" torr (13Nm )] from (h -CjH5)2Fe and unreacted Be(CjH5-h ,h )2. 

Several types of supramolecular self-assembly are found in indenyl and fluorenyl complexes of the alkali metals. It has recently become possible for the first time to elucidate the crystal structures of unsolvated lithium indenide, [LiC9H7] , 26, and sodium fluorenide, [NaCoHgjn, 27 [24]. The crystal structure of 26 closely resembles that of unsolvated lithium cyclopentadienide because it also consists of a polymeric multidecker array in which the Li atoms are symmetrically coordinated by two rj -cyclopentadienyl rings of the indenyl ligands. In contrast, unsolvated sodium fluorenide, 27, forms a two-dimensional supramolecular structure in the solid state (Figure 7.3). In this unusual coordination polymer both the five- and six-membered rings of the fluorene system participate in coordination to sodium via and rj -interactions, respectively. 

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