| Summary: | Although 1,2σ<sup>5</sup>λ<sup>5</sup>-oxaphosphetanes have been known for a long time, the “low-coordinate” 1,2σ<sup>3</sup>λ<sup>3</sup>-oxaphosphetanes have only been known since their first synthesis in 2018 via decomplexation. Apart from ligation of this P-heterocycle to gold(I)chloride and the oxidation using <i>ortho</i>-chloranil, nothing on their chemistry has been reported so far. Herein, we describe the synthesis of new 1,2σ<sup>3</sup>λ<sup>3</sup>-oxaphosphetane complexes (<b>3a</b>–<b>e</b>) and free derivatives (<b>4a</b>–<b>e</b>), as well as reactions of <b>4a</b> with chalcogens and/or chalcogen transfer reagents, which yielded the <i>P</i>-chalcogenides (<b>14</b>–<b>16a</b>; Ch = O, S, Se). We also report on the theoretical results of the reaction pathways of <i>C</i>-phenyl-substituted 1,2 σ<sup>3</sup>λ<sup>3</sup>-oxaphosphetanes and ring strain energies of 1,2σ<sup>4</sup>λ<sup>5</sup>-oxaphosphetane <i>P</i>-chalcogenides.
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