Halogenation of Diphosphorus Complexes.

A systematic study of diverse halogenation reactions of the tetrahedral MoP ligand complex [{CpMo(CO)}(μ,η:η-P)] () is reported. By reacting with different halogenating agents, a series of complexes such as [(CpMo)(μ-P)(μ-PI)(μ-I)(I)(I)] (), [{CpMo(CO)}(μ-PBr)] (), [{CpMo(CO)}(CpMoBr)(μ-PBr)] (), [{CpMo(CO)}(μ-PCl)] (), and [{CpMo(CO)}(CpMoCl)(μ-PCl)] () were obtained. Whereas the reaction of toward various bromine and chlorine sources leads to similar results, a different behavior is observed in the reaction with iodine in which is formed. The products were comprehensively characterized by spectroscopic methods and single crystal X-ray diffraction, and the electronic structures of , , and were elucidated by DFT calculations.