| Summary: | <p>The use of a bis(diphenyl)phosphine functionalized β‐diketiminato ligand, [HC{(CH<sub>3</sub>)C}<sub>2</sub>{(<em>ortho</em>‐[P(C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>]<sub>2</sub>C<sub>6</sub>H<sub>4</sub>)N}<sub>2</sub>]<sup>−</sup> (PNac), as a support for germanium(II) and tin(II) chloride and phosphaketene compounds, is described. The conformational flexibility and hemilability of this unique ligand provide a versatile coordination environment that can accommodate the electronic needs of the ligated elements. For example, chloride abstraction from [(PNac)ECl] (E=Ge, Sn) affords the cationic germyliumylidene and stannyliumylidene species [(PNac)E]<sup>+</sup> in which the pendant phosphine arms associate more strongly with the Lewis acidic main group element centers, providing further electronic stabilization. In a similar fashion, chemical decarbonylation of the germanium phosphaketene [(PNac)Ge(PCO)] with tris(pentafluorophenyl)borane affords a “push–pull” stabilized phosphinidene in which one of the phosphine groups of the ligand backbone associates with the low valent phosphinidene center.</p>
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