Lanthanide elements organometallic compounds

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. 

As a group of typical metal elements, lanthanide elements can form chemical bonds with most nonmetal elements. Some low-valence lanthanide elements can form chemical bonds in organometallic or atom cluster compounds. Because lanthanide elements lack sufficient electrons and show a strong repulsive force towards a positive charge, chemical bonds between lanthanide metals have not yet been observed. Table 1.4 shows that 1391 structure-characterized lanthanide complexes were reported in publications between 1935 and 1995 and these are sorted by chemical bond type. 

Cerium is the only lanthanide element forming tetravalent compounds, stable in aqueous solutions, because the ion Ce + has the electron configuration of the ideal gas xenon. Despite the very strong oxidizing power of the Ce cation, several organometallic compounds have been reported to have an astonishingly high stability. 

The organometallic chemistry of lanthanides is much more limited than in the d block. Compounds such as (C5H5)3Ln and (C5H5)2LnX (X = Cl, H, etc.) have more ionic character than for transition elements,... 

Although lacking 7T-bonded compounds in low oxidation states that characterize the d-block elements, the actinides have a rich organometallic chemistry. Their compounds frequently exhibit considerable thermal stability, but like the lanthanide compounds are usually intensely air- and moisture-sensitive. They are often soluble in aromatic hydrocarbons such as toluene and in ethers (e.g., THF) but are generally destroyed by water. Sometimes they are pyrophoric on exposure to air. Most of the synthetic work has been carried out with Th and U this is partly due to the ready availability of MCI4 (M = Th, U) and also because of the precautions that have to be taken in handling compounds of other metals, especially Pu and Np. 

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