Synthesis,Structure,and Hydrophosphorylation of pi-Complexes Derived from tert-Butyl(l,3-dimethyl-2-butenylidene)amine and Homoligand Iron(O)and Group Vib Metal Carbonyls

摘要

New iron(O),chrornium(O),molybdenum(O),and tungsten(O)pi-complexes containing eta~2-,eta~3-,and eta4-coordinated fcrt-butyl(l,3-dimethyl-2-butenylidene)arnine 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 pi-complexes reacted with dialkyl phosphonates in the presence of triethylamine to afford organometallic alpha-aminophosphonates;hydrophosphorylation in the absence of a catalyst gave the corresponding amidophosphate which then underwent rearrangement into alpha-aminophosphonate.