Alkyl complexes small molecule insertion

Another class of heteroleptic alkyl complexes contains 7t-donating ancillary ligands such as RU[N(Si(CH3)3)2]3 (R = CH3, H, BH ). The hydride species can be converted into the methyl species via reaction with BuLi and CH3Br. The methyl compound has exhibited insertion chemistry with small molecules including aldehydes, ketones, nitriles, and isocyanides (206). Stable metallacyde compounds are also known, ie,... 

The pincer like diamino functionalised carbene ligand stabilises the group 4 metal sufficiently to perform a few very interesting insertion reactions with the M-Me bond. The reactions were performed with the hafnium rather than the zirconium complexes [113]. Small molecules used for these insertion reactions include isonitriles (aryl and alkyl) and CO (see Figure 4.36). Reaction of the hafnium carbene dimethyl complex with xylyl-isonitrile results in addition of this excellent donor ligand and subsequent insertion into the Hf-Me... 

Lanthanide alkyl and aryl complexes can readily react with a range of substrates with acidic protons, such as alcohols, phenols, phenylacetylene, and amine, to be converted into the corresponding lanthanide derivatives. Lanthanide alkyl complexes react with H2 to form the corresponding hydride complex, which is the popular route to lanthanide hydride. Various unsaturated small molecules can insert into an Ln-alkyl bond to form the derivates containing Ln-heteroatom bonds. The reaction modes found are summarized in Figure 8.14 [59-62]. 

Insertion of small molecules into the Pt-G bond is an important fundamental reaction of alkyl complexes. The acetylplatinum(ii) complex with the 2-picolinate ligand 81 is formed via reaction of CO with the methyl complex. 

These / -elimination-resistant alkyl complexes 66 present an interesting reactivity toward insertion reaction such as with CO, leading to a 17-electron acyl(carbonyl) complex 68 (see Equation (6)). Other small unsaturated organic molecules have been used by Akita s group, but only phenylacetylene has led to C-C bond formation, affording, after hydrolysis of the solution, a mixture of -phenyl-1-butene with 68% yield. 

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