%0 Journal Article
%A Frazier, Brenda
A.
%A Wolczanski, Peter T.
%A Keresztes, Ivan
%A DeBeer, Serena
%A Lobkovsky, Emil B.
%A Pierpont, Aaron W.
%A Cundari, Thomas R.
%D 2016
%T Synthetic Approaches to
(smif)2Ti (smif
= 1,3-di-(2-pyridyl)-2-azaallyl) Reveal Redox Non-Innocence and C–C
Bond-Formation
%U https://acs.figshare.com/articles/journal_contribution/Synthetic_Approaches_to_smif_sub_2_sub_Ti_smif_1_3_di_2_pyridyl_2_azaallyl_Reveal_Redox_Non_Innocence_and_C_C_Bond_Formation/2498947
%R 10.1021/ic300590t.s001
%2 https://ndownloader.figshare.com/files/4141822
%K XAS
%K 4. Calculations support
%K Synthetic Approaches
%K ligand radicals
%K smif
%K redox noninnnocent
%K NMR spectroscopy
%K dianion ligands
%X Attempted syntheses of (smif)2Ti (smif =1,3-di-(2-pyridyl)-2-azaallyl)
based on metatheses of TiClnLm (n = 2–4) with M(smif) (M
= Li, Na), in the presence of a reducing agent (Na/Hg) when necessary,
failed, but several apparent Ti(II) species were identified by X-ray
crystallography and multidimensional NMR spectroscopy: (smif){Li(smif-smif)}Ti
(1, X-ray), [(smif)Ti]2(μ-κ3,κ3-N,N(py)2-smif,smif) (2), (smif)Ti(κ3-N,N(py)2-smif,(smif)H)
(3), and (smif)Ti(dpma) (4, dpma = di-2-pyridylmethyl-amide). NMR spectroscopy
and K-edge XAS showed that each compound possesses ligands that are
redox noninnnocent, such that d1 Ti(III) centers AF-couple
to ligand radicals: (smif){Li(smif-smif)2–}TiIII (1), [(smif2–)TiIII]2(μ-κ3,κ3-N,N(py)2-smif,smif) (2), [(smif2–)TiIII](κ3-N,N(py)2-smif,(smif)H)
(3), and (smif2–)TiIII(dpma)
(4). The instability of (smif)2Ti relative
to its C–C coupled dimer, 2, is rationalized via
the complementary nature of the amide and smif radical dianion ligands,
which are also common to 3 and 4. Calculations
support this contention.
%I ACS Publications