Abstract: | The Reactions of tBu2P–P=P(Me)tBu2 and (Me3Si)tBuP–P=P(Me)tBu2 with PR3 tBu2P–P=P(Me)tBu2 ( 1 ) reacts at 20 °C with PMe3, PEt3, P(c‐Hex)3, P(p‐Tol)3, PPh2Me, PPh2Et, PPhEt2, PPh2iPr, PPh3 and P(NEt2)3 yielding tBu2P–P=PR3 and tBu2PMe; however, PtBu3, PtBu2(SiMe3) and tBu2PCl don't. tBu2PH and 1 form tBu2P–PH–PtBu2 which yields tBu2P–P=PEt3 when treated with PEt3. Ph2PH, tBuPH2, PH3, Ph2PCl and EtOH don't substitute the tBu2PMe group in 1 , instead, the molecule is decomposed. With PEt3, (Me3Si)tBuP–P=P(Me)tBu2 forms (Me3Si)tBuP–P=PEt3. The compounds tBu2P–P=PR3 decompose at 20 °C to different degrees giving P‐rich consecutive products of the phosphinophosphinidene. |