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One at a time: Stepwise opening and final removal of the η1‐bound Cp* substituents in the bridged pentelidene complexes [Cp*E{W(CO)5}2] (E=P, As) occurs by the reaction with primary phosphines. Not only novel diphospha‐ and arsaphosphanorbornenes are obtained, but also diastereomerically pure complexed triphosphines. All reaction steps were monitored by NMR spectroscopy, and compounds structurally...
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