Lithium transition metal halides

See Lithium nitride Transition metal halides Sulfur nitrides... 

This method, sometimes referred to as transmetallation, is by far the most versatile synthetic route to transition metal amide complexes. The amide, typically lithium or sodium, is reacted with the corresponding transition metal halide either in a hydrocarbon or, more typically, an ether solvent. The method has been applied to virtually all of the transition elements and normally results in complete substitution except for the most bulky amido substituents (equations 12,37 13,38 14,39 1540... 

Boroles are readily reduced to the respective dianions owing in part to the empty p orbital on the boron atom. The reduction of 6-(4-/i< t/-butylphenyl)-3-/i t/-butyl-5-(bis-2,6-(4-/< /r-butylphenyl)phenyl)dibenzoborole 37 with excess lithium powder in diethyl ether suspension at — 10°C led to deep red crystalline dianionic bis(diethylether)dilithium salt 38. An attempt to obtain transition metal complexes by metathesis reactions of transition metal halides SnCU,... 

Lithium hydride, prepared by hydrogenolysis of /-butyllithium under pressure, was observed to reduce aldehydes and cyclohexanones to the corresponding alcohols in the presence of transition metal halides.An equimolar quantity of vanadium trichloride was found to be the most effective catalyst, but the identity of the active reducing species was not established. 

The catalysts described above were prepared via low temperature precipitation from non-aqueous solution (J). This technique involves the precipitation of the transition metal sulfide from a non-aqueous solvent such as ethyl acetate by dissolving the appropriate transition metal halide in the solvent and reacting it metathetically with a sulfiding agent such as lithium sulfide to precipitate the insoluble sulfide for example ... 

Use of main-group metal silyls to prepare transition-metal silyls appears to be a generally applicable method that is primarily limited by the availability of suitable starting materials, since these silyl anion reagents are sometimes rather difficult to obtain. Typically an alkali-metal silyl is generated in solution and then treated with the appropriate transition-metal halide. Displacement of halide by the silyl anion, with salt elimination, then leads to product (equations 17-19)46 49. The lithium silyl in equation... 

Wilkinson and coworkers obtained stable alkyl complexes by the reaction of transition metal halides or complex halides with trimethylsilylmethyl lithium 72 With these alkyl complexes, no /3-elimination reaction proceeds. The action of Grignard or organolithium reagents on halogen complexes of Pt(II) and Pd (II) has been widely used for the preparation of alkyl complexes, and quite stable alkyl complexes of noble metals can be prepared 73K... 

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