Lanthanide organometallics alkyls

Surface organometallic chemistry with rare-earth metals (or lanthanides) on various inorganic oxides has advanced considerably during the past decade but is still in its infancy. A major drawback has been the difficult access and handling of pure (homoleptic) Ln alkyl precursors with reactive Ln-C(alkyl) bonds [101]... 

The historical sketch outlines the class of lanthanide amides this article is to deal with and which is further manifested in Scheme 1. Organometallic amides which can be classified as dialkyl (-aryl, -silyl) amides and amides derived from unsaturated heterocyclic ligands are seen with respect to N-unsubstituted (primary, inorganic) amides. The consideration of more classic coordination compounds like acid amides or sulfonamides, often ascribed as wet chemistry , is excluded. The historical data also demonstrate the relatively late start of lanthanide amide chemistry reflecting the late industrial establishment of the lanthanide elements (separation, purification, etc.) [9], However, lanthanide amides are still the youngest class in conjunction with the most important pillars of organometallic lanthanide chemistry, namely the alkyls/cyclopentadienyls (LnCp3, 1954, [10]) and the alkoxides (Ce(OR)4 1956 [11a] La(OR)3 , 1958 [lib]). Indeed most of the work has been conducted in the last ten years. 

In summary, the special combination of physical properties of the lanthanides should translate into novel and potentially useful chemical behaviour. As stated in an earlier summary of organolanthanide chemistry 14), the challenge in the lanthanide area, therefore, is to place the lanthanide metals in chemical environments which allow exploitation of their chemical uniqueness. In the past 5 years, organometallic environments beyond the simple, original, tris(cyclopentadienyl) and bis(cyclo-pentadienyl) chloride and alkyl types have been explored and some remarkable chemistry has resulted. 

Except for a 1960 report on one alkylaluminum system 104), no /3-alkyl elimination reactions of this type had ever been observed. Thus, this reaction provided another example in which lanthanide systems demonstrated special organometallic chemistry. 

In this article the term organometallic compound includes alkyl and aryl derivatives of the rare earths—the transition metals of group III, scandium, yttrium, lanthanum and the lanthanides cerium to liitetium with covalent metal-to-carbon a-bonds, as well as the so-called 77-complexes with more than monohapto metal-to-carbon bonds, for example cyclopentadienyl and olefin complexes, metal acetylides, but not carbonyls, cyanides and isocyanide complexes. Derivatives of scandium, yttrium and lanthanum are included and discussed together with the compounds of the lanthanides, because of many similarities in the synthesis and the chemistry of these organometallic derivatives of the rare earths. 

---