A “push–pull” stabilized phosphinidene supported by a phosphine‐functionalized β‐diketiminato ligand

<p>The use of a bis(diphenyl)phosphine functionalized &beta;‐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</...

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التفاصيل البيبلوغرافية
المؤلفون الرئيسيون: Bestgen, S, Mehta, M, Johnstone, TC, Roesky, PW, Goicoechea, JM
التنسيق: Journal article
اللغة:English
منشور في: Wiley 2020
الوصف
الملخص:<p>The use of a bis(diphenyl)phosphine functionalized &beta;‐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>&minus;</sup>&nbsp;(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>&nbsp;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 &ldquo;push&ndash;pull&rdquo; stabilized phosphinidene in which one of the phosphine groups of the ligand backbone associates with the low valent phosphinidene center.</p>