Reaction of Li/Cl phosphinidenoid Fe(CO) 4 complex 2 with ammonia and different amines R 1 ,R 2 NH yielded complexes 3-5 (3: R 1 = R 2 = H; 4a: R 1 = H, R 2 = Me; 4b: R 1 = H, R 2 = iPr; 4c: R 1 = H, R 2 = tBu; 4d: R 1 = H, R 2 = allyl; 4e: R 1 = H, R 2 = Ph; 5: R 1 = Me, R 2 = Me) having 1,1′-bifunctional phosphane ligands via formal N-H bond insertion of the phosphorus center. Studies on deprotonation enabled access to the first struc- [a]

Reactions of a μ2-(η1,η2)-dinuclear diphosphene tungsten(0) complex with DMAD, PTAD and DEAD was applied to P-heterocyclic synthesis, thus combining a singlet carbene-type and a nucleophilic reactivity of a homonuclear π-system.

1,2-Bifunctional ligands are rare, in general, which holds especially for those with a P-N linkage. Herein, we report on the synthesis of P-tert-butyl substituted aminophosphane W(CO)5 complexes 3a-f (a: R = R’ = H; b: R = H, R = Me; c: R = H, R’ = ally; d: R = H, R’ = i-Pr; e: R = H, R’ = t-Bu; f: R = R’ = Me) obtained via formal N-H insertion reactions of Li/Cl phosphinidenoid complex 2 into NH bonds of ammonia and different amines. The 1,2-bifunctionality of 3b was addressed in targeted regioselective deprotonation reactions leading to amidophosphane complexes M-4b or M/N(H)Me phosphinidenoid complexes M-5b, respectively (M = Li, K). Remarkable was the observation that reactions of M-4b and M-5b with MeI as the electrophile resulted in the formation of the same product 7b. The constitution of all the compounds has been established by means of NMR and IR spectroscopy and mass spectrometry. Two possible reaction pathways were studied in detail using high-level DFT calculations.