1,2σλ-Oxaphosphetanes and Their -Chalcogenides-A Combined Experimental and Theoretical Study.

Although 1,2σλ-oxaphosphetanes have been known for a long time, the "low-coordinate" 1,2σλ-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 -chloranil, nothing on their chemistry has been reported so far. Herein, we describe the synthesis of new 1,2σλ-oxaphosphetane complexes (-) and free derivatives (-), as well as reactions of with chalcogens and/or chalcogen transfer reagents, which yielded the -chalcogenides (-; Ch = O, S, Se). We also report on the theoretical results of the reaction pathways of -phenyl-substituted 1,2 σλ-oxaphosphetanes and ring strain energies of 1,2σλ-oxaphosphetane -chalcogenides.