Abstract
AbstractPhosphonio‐benzo[c]phospholides with an additional phosphonium ylide substituent in 3‐position were synthesized by deprotonation of appropriately substituted 1, 3‐bis‐phosphonio benzophospholide cations and characterized by spectroscopic and analytical data. The ability of these molecules to act as bidentate P, C‐chelating ligands to transition metal atoms was demonstrated in the reactions with [W(CO)4(norbornadiene)] and [MCl2(cyclooctadiene)] (M = Pd, Pt). The PdII and PtII complexes are distinguished by a strong inclination towards addition of H2O to the 10π‐electron system of the ligand. The molecular structures of a W0 complex with a P, C‐chelating ylidyl‐phosphonio‐benzophospholide ligand and of the product resulting from H2O‐addition to a corresponding PtII complex were determined. The structural parameters of the W0 complex provide evidence for the presence of substantial steric strain around the metal atom.
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