Synthetic Approaches to (smif)₂Ti (smif=1,3-di-(2-pyridyl)-2-azaallyl) Reveal Redox Non-Innocence and C-C Bond-Formation

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Article discussing synthetic approaches to (smif)₂Ti(smif=1,3-di-(2-pyridyl)-2-azallyl) revealing redox non-innocence and C-C bond-formation.

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10 p.: ill.

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Frazier, Brenda A.; Wolczanski, Peter T.; Keresztes, Ivan; DeBeer, Serena 1973-; Lobkovsky, Emil B.; Pierpont, Aaron W. et al. July 25, 2012.

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Article discussing synthetic approaches to (smif)₂Ti(smif=1,3-di-(2-pyridyl)-2-azallyl) revealing redox non-innocence and C-C bond-formation.

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10 p.: ill.

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Reprinted with permission from the Inorganic Chemistry journal. Copyright 2012 American Chemical Society.

Abstract: Attempted syntheses of (smif)₂Ti(smif=1,3-di-(2-pyridyl)-2-azaallyl) based on metatheses of TiClɴLм (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 noninnocent, such that d¹Ti(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.

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  • Inorganic Chemistry, 2012, Washington DC: American Chemical Society, pp. 8177-8186

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  • Publication Title: Inorganic Chemistry
  • Volume: 51
  • Issue: 15
  • Page Start: 8177
  • Page End: 8186
  • Peer Reviewed: Yes

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  • July 25, 2012

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  • Aug. 30, 2013, 3:35 p.m.

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Frazier, Brenda A.; Wolczanski, Peter T.; Keresztes, Ivan; DeBeer, Serena 1973-; Lobkovsky, Emil B.; Pierpont, Aaron W. et al. Synthetic Approaches to (smif)₂Ti (smif=1,3-di-(2-pyridyl)-2-azaallyl) Reveal Redox Non-Innocence and C-C Bond-Formation, article, July 25, 2012; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc179684/: accessed August 18, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.