Browsing by Subject "Oxidation"

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    1,2σ3λ3-Oxaphosphetanes and Their P-Chalcogenides ¿ A Combined Experimental and Theoretical Study
    (2022-05-23) Gleim, F.; Garcia Alcaraz, A.; Schnakenburg, G.; Espinosa Ferao, A. F.; Streubel, R.; Química Orgánica
    Although 1,2σ 5λ 5 -oxaphosphetanes have been known for a long time, the “low-coordinate” 1,2σ 3λ 3 -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 1,2σ 3λ 3 - 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 σ 3λ 3 - oxaphosphetanes and ring strain energies of 1,2σ 4λ5 -oxaphosphetane P-chalcogenides.
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    Dihaloperhaloaryl triphenylarsine gold(III) complexes
    Usón, Rafael; Laguna, Antonio; Vicente, José; Química Inorgánica; Química Inorgánica de la Universidad de Zaragoza
    When C6CISAuAsPh3 reacts with halogens, oxidation of the gold(I) complex and formation of X2Au(C6C15)AsPh3 (X = Cl, Br, I) take place. However, when C6F5AuAsPh3 reacts with halogens, oxidation is only observed in the case of Cl2 whilst I2 (totally) and Br2 (partially) split the Au-C bond. This behaviour is contrary to that observed with C6F5AuPPh3 and halogens, where the tendency to split the Au-C bond decreases in the sequence C! > Br > I.