Abstract
Abstract Stimulated by the successful generation of unsaturated molecules with low-coordinated phosphorus centers by heterogeneous surface dechlorination, CI2,P[sbnd]C[tbnd]C[sbnd]PCI2, is synthesized and characterized by PE and mass spectra. In addition, [Mg] curls, [Ag] wool and catalysts [Cux/TiO2] or [MgCI2,[sbnd]MgO/SiO2] are tested as potential dechlorinating agents for phosphorus halides like OPCI3, SPCI3, H3C[sbnd]PCI2, H5C2-PCI2, (H3C)3C[sbnd]PCI2, or H5C6-PCI2, in a gasflow reactor under reduced pressure and yield, inter aha, the following representative results: due to the thermodynamically favored formation of [MgCl2], [MgO] or [MgS] at the Mg surface, P4 is the only gaseous product identified from reactions of OPCI3, and SPCI3, with [Mg] metal at higher temperatures. On the contrary, passing H3C-PCI2, at 600K over [Mg] yields a reaction mixture containing P(CH3)3,(H3C)2P[sbnd]P(CH3)2, (H3C[sbnd]P), and CH4, which suggests an intermediate formation of surface phosphinidenes [H3C[sbnd]P →Mg]. A...
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