Transition-metal-substituted diphosphenes. XVII. Dipolar [3 + 2] cycloadditions of carbonyl-activated alkynes to (h5-C5Me5)(CO)2Ru-P=P-aryl (aryl = 2,4,6-tBu3C6H2). First examples of s/p-rearrangements of diphosphene ligands.
The reaction of (h5-C5Me5)(OC)2RuP:PR [I, R = 2,4,6-(Me3C)3C6H2] with Me 2-butynoate yielded the five-membered metallaheterocycle II with an (E)-configurated exocyclic P:P bond. On the other hand, the similarly formed cycloadduct, obtained from I and MeO2CC.tplbond.CCO2Me at -78 Deg, rapidly underwent a s/p rearrangement to the complex III featuring a h2-coordinated P:P unit. The mol. structure of III was established by single-crystal x-ray diffraction anal.
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