Abstract
Reduction of tetraphenylphosphonium bromide with LiAlH(D)4 at room temperature affords first the monohydrophosphorane Ph4PH, then the dihydrophosphoranate anion Ph4PH2]− which decomposes to the dihydrophosphorane Ph3PH2, all of which are identified by 31PNMR. Reductions of other phosphonium salts appear to follow a similar path. At elevated temperatures none of these intermediates is observed and attempted isolation leads to extensive decomposition.
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