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The selective deselenation of the recently described tetraphosphatetracycle 4a leads to the tetraphosphabishomoprismane 6 in high yield. Triethylphosphine is used as a deselenating reagent. A further example for a selective decomposition of 4a is performed by mesitylnitrile oxide (9), yielding the 1,2,4-oxazaphosphole 10. Bromine and iodine furnish tetracyclic rearrangement products 13a,b. Finally, the applicability of the tetracycle 4a as a ligand in transition metal chemistry is evaluated by complexation with tungsten (14) and, respectively, iron (15) carbonyl fragments. Side aspects of this article are the first synthesis of 3,5-dimesityl-1,2,4-selenadiphosphole 2e starting from mesitylphosphaalkyne 1e, as well as the first report on a mixed substitution at a cage compound of type 4. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:406–413, 2001 |
