Abstract
Stable syn-substituted methylenediphosphirane complexes are obtained from the reaction of transient, electrophilic phosphinidenes [R-PdW(CO)5] (R ) Me, Ph), thermally generated from the corresponding benzophosphepines, with 1-phosphaallene. A DFT analysis at the B3PW91/6-31G(d) level of theory reveals that the high diastereoselectivity of this reaction results from the preferred negative activation energy
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