Controlled scrambling reactions to polyphosphanes via bond metathesis reactions

Triphosphanes R'₂PP(R)PR'₂ (9a,c: R = Py; 9b R = BTz), 1,3-diphenyl-2-pyridyl-triphospholane 9d and pentaphospholanes (RP)₅ (13: R = Py; 18: R = BTz) are obtained in high yield of up to 98% from the reaction of dipyrazolylphosphanes RPpyr₂ (5: R = Py; 6: R = BTz; pyr = 1,3-dimethylpyrazolyl) and the respective secondary phosphane (R'₂PH, R' = Cy (9a,b), Bu (9c); PhPH(CH₂)₂PHPh (9d)). The formation of derivatives 9a-d proceeds via a condensation reaction while the formation of 13 and 18 can only be explained by a selective scrambling reaction. We realized that the reaction outcome is strongly solvent dependent as outlined by the controlled scrambling reaction pathway towards pentaphospholane 13. In our further investigations to apply these compounds as ligands we first confined ourselves to the coordination chemistry of triphosphane 9a with respect to coinage metal salts and discussed the observation of different syn- and anti-isomeric metal complexes based on NMR and X-ray analyses as well as quantum chemical calculations. Methylation reactions of 9a with MeOTf yield triphosphan-1-ium Cy₂MePP(Py)PCy₂ ⁺ (10 ⁺) and triphosphane-1,3-diium Cy₂MePP(Py)PMeCy₂ ²⁺ (11 ²⁺) cations as triflate salts. Salt 11[OTf]₂ reacts with pentaphospholane 13 in an unprecedented chain growth reaction to give the tetraphosphane-1,4-diium triflate salt Cy₂MePP(Py)P(Py)PMeCy₂ ²⁺ (19[OTf]₂) via a P-P/P-P bond metathesis reaction. The latter salt is unstable in solution and rearranges via a rare [1,2]-migration of the Cy₂MeP-group followed by the elimination of the triphosph-2-en-1-ium cation [Cy₂MePPPMeCy₂]⁺ (20 ⁺) to yield a novel 1,4,2-diazaphospholium salt (21[OTf]).