Halogenation of Diphosphorus Complexes
journal contribution
posted on 2021-03-18, 16:39 authored by Anna Garbagnati, Michael Seidl, Gábor Balázs, Manfred ScheerA systematic study of diverse halogenation
reactions of the tetrahedral
Mo<sub>2</sub>P<sub>2</sub> ligand complex [{CpMo(CO)<sub>2</sub>}<sub>2</sub>(μ,η<sup>2</sup>:η<sup>2</sup>-P<sub>2</sub>)] (<b>1</b>) is reported. By reacting <b>1</b> with
different halogenating agents, a series of complexes such as [(CpMo)<sub>4</sub>(μ<sub>4</sub>-P)(μ<sub>3</sub>-PI)<sub>2</sub>(μ-I)(I)<sub>3</sub>(I<sub>3</sub>)] (<b>2</b>), [{CpMo(CO)<sub>2</sub>}<sub>2</sub>(μ-PBr<sub>2</sub>)<sub>2</sub>] (<b>3a</b>), [{CpMo(CO)<sub>2</sub>}(CpMoBr<sub>2</sub>)(μ-PBr<sub>2</sub>)<sub>2</sub>] (<b>4a</b>), [{CpMo(CO)<sub>2</sub>}<sub>2</sub>(μ-PCl<sub>2</sub>)<sub>2</sub>] (<b>3b</b>),
and [{CpMo(CO)<sub>2</sub>}(CpMoCl<sub>2</sub>)(μ-PCl<sub>2</sub>)<sub>2</sub>] (<b>4b</b>) were obtained. Whereas the reaction
of <b>1</b> toward various bromine and chlorine sources leads
to similar results, a different behavior is observed in the reaction
with iodine in which <b>2</b> is formed. The products were comprehensively
characterized by spectroscopic methods and single crystal X-ray diffraction,
and the electronic structures of <b>2</b>, <b>3a</b>,
and <b>4a</b> were elucidated by DFT calculations.
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