Über die Oxo‐cyclotetraphosphane (PBut)4O1–4 |
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Authors: | M. Baudler A. Michels M. Michels |
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Abstract: | Contributions to the Chemistry of Phosphorus. 243 On the Oxocyclotetraphosphanes (PBut)4O1–4 Under suitable conditions, the reaction of tetra‐tert‐butylcyclotetraphosphane, (PBut)4, with dry atmospheric oxygen gives rise to the corresponding monoxide (PBut)4O ( 1 ) which has been isolated by column chromatography. The reaction with hydrogen peroxide furnishes a mixture of oxocyclotetraphosphanes (PBut)4O1–4 consisting of two constitutionally isomeric dioxides (PBut)4O2 ( 2 a , 2 b ), the trioxide (PBut)4O3 ( 3 ), and the tetraoxide (PBut)4O4 ( 4 ), in addition to 1 . According to the 31P NMR parameters the oxygen atoms are exclusively exocyclically bonded to the phosphorus four‐membered ring. Which of the P atoms are present as λ5‐phosphorus follows from the different low‐field shifts of the individual P nuclei compared with the starting compound. Accordingly, 1 is 1,2,3,4‐Tetra‐tert‐butyl‐1‐oxocyclotetraphosphane, 2 a and 2 b are 1,2,3,4‐Tetra‐tert‐butyl‐1,2‐dioxo‐ and ‐1,3‐dioxocyclotetraphosphane, respectively, 3 is 1,2,3,4‐Tetra‐tert‐butyl‐1,2,3‐trioxocyclotetraphosphane, and 4 is 1,2,3,4‐Tetra‐tert‐butyl‐1,2,3,4‐tetraoxocyclotetraphosphane. When the oxidation reaction proceeds a fission of the P4 ring takes place. |
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Keywords: | Phosphanes Cyclophosphane Oxides 1,2,3,4Tetra‐tert‐butyl‐1‐oxocyclotetraphosphane 1,2,3,4‐Tetra‐tert‐butyl‐1,2‐dioxocyclotetraphosphane 1,2,3,4‐Tetra‐tert‐butyl‐1,3‐dioxocyclotetraphosphane 1,2,3,4‐Tetra‐tert‐butyl‐1,2,3‐trioxocyclotetraphosphane 1,2,3,4‐Tetra‐tert‐butyl‐1,2,3,4tetraoxocyclotetraphosphane |
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