American Chemical Society
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Novel tert-Butyl-tris(3-hydrocarbylpyrazol-1-yl)borate Ligands:  Synthesis, Spectroscopic Studies, and Coordination Chemistry#

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journal contribution
posted on 2006-07-10, 00:00 authored by Olivier Graziani, Paul Hamon, Jean-Yves Thépot, Loïc Toupet, Petra Á. Szilágyi, Gábor Molnár, Azzedine Bousseksou, Mats Tilset, Jean-René Hamon
The lithium (1) and thallium (2) salts of five new tert-butyl-tris(3-hydrocarbylpyrazol-1-yl)borate ligands [t-BuTpR]- (R = H, a; Me, b; i-Pr, c; t-Bu, d; Ph, e) have been synthesized and characterized. Because of steric congestion at B, the reaction between t-BuBH3Li·0.5Et2O and excess 2,5-dimethylpyrazole HpzMe2 afforded the bis-pzMe2 derivative, Tl[t-BuBH(3,5-Me2pz)2] (3) after metathesis with TlNO3. The compounds were characterized by elemental analysis and NMR spectroscopy. The Li salts 1a and 1c exhibit fluxional behavior on the NMR time scale in solution at room temperature. The solid-state 7Li and 11B NMR spectra of 1c suggest that this salt exists as a mixture of axial and equatorial isomers. The partial hydrolysis of 1d afforded the dimeric Li complex {Li[t-BuB(pzt-Bu)2(μ-OH)]}2 (4). The crystal structure of 4 shows two Li cations encapsulated by the heteroscorpionate [t-BuB(OH)(3-t-Bupz)2]- ligands. A salt elimination reaction between FeCl2(THF)1.5 and 2 equiv of Li[t-BuTpR] (R = H, Me) followed by an in situ one-electron oxidation produced good yields of the homoleptic, paramagnetic low-spin iron(III) complexes [Fe(t-BuTp)2]PF6 (5) and [Fe(t-BuTpMe)2]PF6 (6) that were characterized by elemental analyses, magnetic susceptibility measurements in solution and the solid phase, 1H NMR, high-resolution mass spectrometry, Mössbauer spectroscopy, and single-crystal X-ray diffraction. The crystals are composed of discrete molecular units with the central Fe(III) ion in an almost perfectly octahedral coordination to six nitrogen atoms. Compound 5 has the shortest Fe−N bond lengths ever reported for [Fe(RTpR‘)2]+-type compounds.