The oxidation of [(Cp*Mo)(2)(mu,eta(6):eta(6)-P-6)] (1) with halogens or halogen sources was investigated. The iodination afforded the ionic complexes [(Cp*Mo)(2)(mu,eta(3):eta(3)-P-3)(mu,eta(1):eta(1):eta(1):eta(1)-P3I3)][X] (X=I-3(-), I-) (2) and [(Cp*Mo)(2)(mu,eta(4):eta(4)-P-4)(mu-PI2)][I-3] (3), while the reaction with PBr5 led to the complexes [(Cp*Mo)(2)(mu,eta(3):eta(3)-P-3)(mu-Br)(2)][Cp*MoBr4] (4) [(Cp*MoBr)(2)(mu,eta(3):eta(3)-P-3)(mu,eta(1)-P2Br3)] (5) and [(Cp*Mo)(2)(mu-PBr2)(mu-PHBr)(mu-Br)(2)] (6). The reaction of 1 with the far stronger oxidizing agent PCl5 was followed via time- and temperature-dependent P-31{H-1} NMR spectroscopy. One of the first intermediates detected at 193 K was [(Cp*Mo)(2)(mu,eta(3):eta(3)-P-3)(mu-PCl2)(2)][PCl6] (8) which rearranges upon warming to [(Cp*Mo)(2)(mu-PCl2)(2)(mu-Cl)(2)] (9), [(Cp*MoCl)(2)(mu,eta(3):eta(3)-P-3)(mu-PCl2)] (10) and [(Cp*Mo)(2)(mu,eta(4):eta(4)-P-4)(mu-PCl2)][Cp*MoCl4] (11), which could be isolated at room temperature. All complexes were characterized by single-crystal X-ray diffraction, NMR spectroscopy and their electronic structures were elucidated by DFT calculations.