Journal
INORGANIC CHEMISTRY
Volume 51, Issue 15, Pages 8177-8186Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic300590t
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Funding
- NSF [CHE-0718030, CHE-1057758]
- Cornell University
- DOE Office of Biological and Environmental Research
- National Institutes of Health, National Center for Research Resources, Biomedical Technology Program [P41RR001209]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1055505] Funding Source: National Science Foundation
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Attempted syntheses of (smif)(2)Ti (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)(mu-kappa(3),kappa(3)-N,N(py)(2)-smif,smif) (2), (smif)Ti(kappa(3)-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 d(1) Ti(III) centers AF-couple to ligand radicals: (smif){Li(smif-smif)(2-)}Ti-III (1), [(smif(2-))Ti-III](2)(mu-kappa(3),kappa(3)-N,N(py)(2)-smif,smif) (2), [(smif(2-))Ti-III](kappa(3)-N,N(py)(2)-smif,(smif)H) (3), and (smif(2-))Ti-III(dpma) (4). The instability of (smif)(2)Ti 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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