Intra- and intermolecular [3+2] cycloaddition reactions of P-Cp*-substituted nitrilium phosphane-ylide tungsten complexes

Thermal ring opening of {pentacarbonyl[2-pentamethylcyclopentadienyl-3-phen yl-2H- azaphosphirene-kappa P]tungsten(0)} (1) in toluene in the presence o f either 1-piperidinonitrile or ethyl cyanoformate yields predominantly tri cyclic P-heterocycle complexes 4a,b via intramolecular trapping reactions o f transiently formed nitrilium phosphane-ylide complexes 3a,b; complex 4a w as isolated and fully characterized. On prolonged heating, complexes 4a,b t ransformed into 2H-1,3,2-diazaphosphole complexes 5a,b, which were also cha racterized by NMR spectroscopy. In the case of 1-piperidinonitrile, acyclic dinuclear complex 6 was formed as byproduct via a 2-fold 1,3-addition reac tion of complex 3a with water. Furthermore, preliminary studies on ring ope ning of complex 4a showed retro-[2+1] and retro-[3+2] cycloaddition reactio ns, depending on the substrate. If dimethyl acetylenedicarboxylate was empl oyed, the tetracyclic phosphorus-carbon cage complex 10 was obtained, and i f 1-piperidinonitrile was used, the 2H-1,3,2-diazaphosphole complex 5a was formed selectively. The structures of 2H-1,3,2-diazaphosphole complex 5a, t he acyclic dinuclear complex 6, and the tetracyclic P-heterocycle complex 1 0 were determined by single-crystal X-ray diffraction.