Lanthanide mono methyls

Bonnet, R Hillier, A. C. Collins, A. Dubberly, S. R. Mountford, R Lanthanide mono(borohydride) complexes of diamide-diamine donor ligands Novel single site catalysts for the polymerisation of methyl methacrylate. Dalton Trans. 2005,421 23. 

The organometallic chemistry of scandium is generally similar to that of the later lanthanides. It thus forms a cyclopentadienyl ScCps that has mixed mono- and pentahapto-coordination like LuCps. An anionic methyl [Li(tmed)]3[M(CH3)6] is formed by scandium, as by the lanthanides. However, there are often subtle differences that should be borne in mind. The pentamethylcyclopentadienyl compound [ScCp 2Me] is a monomer but the lutetium compound is an asymmetric dimer [Cp 2Lu(/u.-Me)LuCp 2Me]. Similarly, whilst triphenylscandium is obtained as a bis(thf) adduct, [ScPh3(thf)2], which has a TBPY structure with axial thf molecules, the later lanthanides form octahedral [LnPh3(thf)3]. Triphenylscandium and the phenyls of the later lanthanides are made by different routes. 

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. 

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