Reactions of with Mixed Anhydrides of Diphenylphosphinous and Acrylic Acids; Structure of (PPh3)(O2CCH2CH2PPh3)>*C4H8O

Article abstract of DOI:10.1039/DT9910002413

Reactions of with 1 mol equivalent of Ph2PO2CCH=CR'R produce (R', R = H or Me), although for R' = H, R = H or Me the major product is (PPh3)(O2CCH2CHR PPh3)>, which for R = H has been crystallographically characterized.Using 2 mol equivalents of Ph2PO2CCR=CR'R the products are (R = H, R' = R = Me; R = Me, R' = H, R = Ph) or .The complexes have all been characterized spectrocopically and the mixed anhydride ligands are generally co-ordinated through P and O, apparently for steric reasons.Binding through P and the C=C appears to occur in , prepared from and Ph2POCH2CH=CMe2, whilst unidentate binding via the P atom is observed for the mixed anhydride in .Crystal data for (PPh3)(O2CCH2CH2PPh3)>: orthorhombic, space group P2₁2₁2₁, with a = 15.16(3), b = 23.05(3), c = 17.08(4) Angstroem and Z = 4.The structure was obtained from 6558 reflections measured on an automatic diffractometer and refined to an R value of 0.076.The main features of the structure include the zwitterionic triphenylphosphoniopropionate betaine ligand binding via the carboxylate in a chelating fashion and the planar RuPOHPO ring of the bis(diphenylphosphinito)hydrogenate ligand.The O...O distance in this ligand is 2.382(12) Angstroem indicative of strong hydrogen bonding.

Full text of DOI:10.1039/DT9910002413

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