Shaffer, David W. Ryken, Scott A. Zarkesh, Ryan A. Heyduk, Alan F. Ligand Effects on the Oxidative Addition of Halogens to (dpp-nacnac<sup>R</sup>)Rh(phdi) The treatment of (dpp-nacnac<sup>R</sup>)­Rh­(phdi) {(dpp-nacnac<sup>R</sup>)<sup>−</sup> = CH­[C­(R)­(N-<sup><i>i</i></sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)]<sub>2</sub><sup>–</sup>; R = CH<sub>3</sub>, CF<sub>3</sub>; phdi = 9,10-phenanthrenediimine} with X<sub>2</sub> oxidants afforded octahedral rhodium­(III) products in the case of X = Cl and Br. The octahedral complexes exhibit well-behaved cyclic voltammograms in which a two-electron reduction is observed to regenerate the initial rhodium­(I) complex. When treated with I<sub>2</sub>, (dpp-nacnac<sup>CH3</sup>)­Rh­(phdi) produced a square pyramidal η<sup>1</sup>-I<sub>2</sub> complex, which was characterized by NMR and UV–vis spectroscopies, mass spectrometry, and X-ray crystallography. The more electron poor complex (dpp-nacnac<sup>CF3</sup>)­Rh­(phdi) reacted with I<sub>2</sub> to give a mixture of two products that were identified by <sup>1</sup>H NMR spectroscopy as a square pyramidal η<sup>1</sup>-I<sub>2</sub> complex and an octahedral diiodide complex. Reaction of the square pyramidal (dpp-nacnac<sup>CH3</sup>)­Rh­(I<sub>2</sub>)­(phdi) with HBF<sub>4</sub> resulted in protonation of the (dpp-nacnac<sup>CH3</sup>)<sup>−</sup> backbone to provide an octahedral rhodium­(III) diiodide species. These reactions highlight the impact that changes in the electron-withdrawing nature of the supporting ligands can have on the reactivity at the metal center. X 2 oxidants;octahedral complexes exhibit;cyclic voltammograms;1 H NMR spectroscopy;mass spectrometry;HBF 4;rhodium;UV;CH;CF;Ligand Effects;Oxidative Addition;octahedral diiodide;metal center 2012-11-19
    https://acs.figshare.com/articles/journal_contribution/Ligand_Effects_on_the_Oxidative_Addition_of_Halogens_to_dpp_nacnac_sup_R_sup_Rh_phdi_/2467609
10.1021/ic300733j.s001