Journal of the American Chemical Society, Vol.117, No.8, 2251-2258, 1995
The Benzodiphosphaalkene Ligand and Its Pd-II and Pt-II Complexes - Their Synthesis, Structure, and an ESR Study of Their Reduction Products
The new diphosphaalkene 1,3-bis[2-(2,4,6-tri-tert-butylphenyl)phosphanediylmethyl]benzeneL has been synthesized. Due to the presence of two P double bond C bonds three isomers (EE, EZ, ZZ) were observed by P-31 NMR, and the crystal structures of two of them could be determined (EE, ZZ). The electrochemical behavior of L has been studied by cyclic voltametry : a quasi-reversible reduction occurs at -1.89 V/SCE and corresponds to the formation of a radical anion which has been studied by ESR at variable temperature. The experimental P-31 and H-1 hyperfine constants are consistent with free rotation about the P double bond C and C-phosphaalkene-C-benzene bonds at room temperature and agree with ab initio predictions. One of the isomers of L forms complexes with palladium(II) and platinum(III) ions. The crystal structures show that L is orthometalated and acts as a terdentate Ligand by coordinating the metal with each phosphorus atom. These complexes are electrochemically reduced between -0.92 and -1.29 V, and the resulting paramagnetic species are studied by ESR in liquid and frozen solutions. This reduction process was shown to be a ligand-centered process, an appreciable part of the unpaired electron is localized on each of the phosphaalkene carbons (20%) and phosphorus atoms (5%).
Keywords:ELECTRON-SPIN-RESONANCE;CRYSTAL-STRUCTURE;BRIDGING LIGAND;NICKEL(II);PALLADIUM(II);LUMINESCENCE;PLATINUM(II);PARAMETERS;DERIVATION;ELEMENTS