Vanadium acetylides

Scheme 28), and vanadium acetylides, formed from acetylenic Grignard or lithium compounds and VCl, react with aldehydes to give a, S-acetylenic ketones via oxidative nucleophilic addition (Scheme... 

Ignition or explosive reaction with metals (e.g., aluminum, antimony powder, bismuth powder, brass, calcium powder, copper, germanium, iron, manganese, potassium, tin, vanadium powder). Reaction with some metals requires moist CI2 or heat. Ignites with diethyl zinc (on contact), polyisobutylene (at 130°), metal acetylides, metal carbides, metal hydrides (e.g., potassium hydride, sodium hydride, copper hydride), metal phosphides (e.g., copper(II) phosphide), methane + oxygen, hydrazine, hydroxylamine, calcium nitride, nonmetals (e.g., boron, active carbon, silicon, phosphoms), nonmetal hydrides (e.g., arsine, phosphine, silane), steel (above 200° or as low as 50° when impurities are present), sulfides (e.g., arsenic disulfide, boron trisulfide, mercuric sulfide), trialkyl boranes. 

Vanadium also forms a very stable carbide VC, and carburization of this metal is part of the corrosion reactions of vanadium based alloys contacted with liquid lithium as well as sodium. Vanadium alloys with contents of titanium have an even higher affinity to form solid carbides by absorbing of carbon from liquid metals. In systems in which vanadium titanium alloys and stainless steels are in contact with the same lithium or sodium, carbon migrates from the steel to the refractory metal alloy, thus passing the alkali metal serving as a transport medium The free energies of formation of the alkali acetylides are compared with the values of several metal carbides in Table V. 

Addition of the acetylide LiCCBu to VClCp2 results in the vanadium alkynide V(CCBu )Cp2 which is the subject of an X -ray crystallographic study. 

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