Oxidation of Li/X phosphinidenoid complex , obtained via selective deprotonation from the P-H precursor , with [Ph3C]BF4 led to the formation of two P-F substituted diorganophosphane complexes 6,; the latter tautomer formed via H-shift from 6. In contrast, oxidation of with [(p-Tol)3C]BF4 led to three major and one minor intermediates at low temperature, which we tentatively assign to two pairs of P-C atropisomers ,a′ and ,c′ and which differ by the relative orientations of their CH(SiMe3)2 and W(CO)5 groups. Conversion of all isomers led finally to complex having a ligand with a long PC bond to the central trityl* carbon atom, firmly established by single-crystal X-ray analysis. DFT calculations at the B3LYP/def2-TZVPP//BP86/def2-TZVP level of theory on real molecular entities revealed the structures of the in situ formed combined singlet diradicals (4+5 and 5+9) and the nature of intermediates on the way to the final product, complex . Remarkable is that all isomers of possess relative energies in the narrow energy regime of about 20 kcal mol−1. A preliminary study revealed that complex undergoes selective PC bond cleavage at 75 °C in toluene solution.