While 1,2σ5λ5-oxaphosphetanes are well known intermediates from the Wittig-reaction, no 1,2σ3λ3-oxaphosphetanes have been described, so far. Herein, we present the first synthesis of 1,2σ3λ3-oxaphosphetanes derived from their κP-Mo(CO)5 complexes and first investigations towards metal coordination and P-oxidation. Bonding, ring strain energy and potential retro-[2+2] cycloaddition reactions of the 1,2-oxaphosphetane ring were studied by DFT methods.
The 1,2-thiaphosphetane heterocycle could be synthesized for the first time in the coordination sphere of a metal complex (I) from which the free ligand (II) could be obtained, too.
Although 1,2σ5λ5-oxaphosphetanes have been known for a long time, the “low-coordinate” 1,2σ3λ3-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 ortho-chloranil, nothing on their chemistry has been reported so far. Herein, we describe the synthesis of new 1,2σ3λ3-oxaphosphetane complexes (3a–e) and free derivatives (4a–e), as well as reactions of 4a with chalcogens and/or chalcogen transfer reagents, which yielded the P-chalcogenides (14–16a; Ch = O, S, Se). We also report on the theoretical results of the reaction pathways of C-phenyl-substituted 1,2 σ3λ3-oxaphosphetanes and ring strain energies of 1,2σ4λ5-oxaphosphetane P-chalcogenides.
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