Selective Derivatization of a Hexaphosphane from Functionalization of White Phosphorus

The reaction of LGa (L = Dipp­(4-(Dipp-imino)­pent-2-en-2-yl)­amide; Dipp: 2,6-diisopropylphenyl) and white phosphorus was revisited. A plethora of unprecedented polyphosphanes in addition to the known monoinserted product LGaP<sub>4</sub> (<b>1</b>) are observed. An optimized synthesis of the hitherto unknown hexaphosphane (LGa)<sub>2</sub>P<sub>6</sub> (<b>3</b>) is presented, and its subsequent selective derivatization with Brønsted acids, MeOTf, Ph<sub>2</sub>ECl (E = P, As), and NaOCP provides access to a wealth of functionalized hexa- and heptaphosphanes.