Abstract

New iron(0), chromium(0), molybdenum(0), and tungsten(0) π-complexes containing η2-, η 3-, and η4-coordinated tert-butyl(1,3-dimethyl-2-butenylidene)amine ligands were synthesized under conditions of photochemical and thermal activation. The geometric, electronic, and energetic parameters of the coordinated 1,3-azadiene were calculated by nonempirical methods, and factors determining the mode of coordination were established. The obtained π-complexes reacted with dialkyl phosphonates in the presence of triethylamine to afford organometallic α-aminophosphonates; hydrophosphorylation in the absence of a catalyst gave the corresponding amidophosphate which then underwent rearrangement into α-aminophosphonate.

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