%0 Journal Article
%A Shaffer, David
W.
%A Ryken, Scott A.
%A Zarkesh, Ryan A.
%A Heyduk, Alan F.
%D 2012
%T Ligand Effects on the
Oxidative Addition of Halogens to (dpp-nacnacR)Rh(phdi)
%U https://acs.figshare.com/articles/journal_contribution/Ligand_Effects_on_the_Oxidative_Addition_of_Halogens_to_dpp_nacnac_sup_R_sup_Rh_phdi_/2467609
%R 10.1021/ic300733j.s001
%2 https://acs.figshare.com/ndownloader/files/4110310
%K X 2 oxidants
%K octahedral complexes exhibit
%K cyclic voltammograms
%K 1 H NMR spectroscopy
%K mass spectrometry
%K HBF 4
%K rhodium
%K UV
%K CH
%K CF
%K Ligand Effects
%K Oxidative Addition
%K octahedral diiodide
%K metal center
%X The treatment of (dpp-nacnacR)Rh(phdi) {(dpp-nacnacR)− = CH[C(R)(N-iPr2C6H3)]2–; R = CH3, CF3; phdi = 9,10-phenanthrenediimine}
with X2 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 I2, (dpp-nacnacCH3)Rh(phdi) produced a square pyramidal
η1-I2 complex, which was characterized
by NMR and UV–vis spectroscopies, mass spectrometry, and X-ray
crystallography. The more electron poor complex (dpp-nacnacCF3)Rh(phdi) reacted with I2 to give a mixture of two products
that were identified by 1H NMR spectroscopy as a square
pyramidal η1-I2 complex and an octahedral
diiodide complex. Reaction of the square pyramidal (dpp-nacnacCH3)Rh(I2)(phdi) with HBF4 resulted in
protonation of the (dpp-nacnacCH3)− 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.
%I ACS Publications