Exploiting the reactivity of actinide fluoride bonds for the synthesis and characterization of a new class of monometallic bis(azide) uranium complexes

Erickson, Karla A.; Lichtscheidl, Alejandro G.; Monreal, Marisa J.; Nelson, Andrew T.; Scott, Brian L.; Morris, David E.; Kiplinger, Jaqueline L.

doi:10.1016/j.jorganchem.2017.10.044

Cited by 2 publications

(1 citation statement)

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“…Besides the versatile application of metal fluorides in catalysis, those complexes are utilized in the synthesis, taking advantage of the high affinity between F and Si atoms. Thus, the reaction between L n M–F and Me 3 Si–R allows the substitution of fluorine by a wide variety of R groups under mild conditions. − The volatile byproduct, Me 3 SiF, can be easily traced by 29 Si and 19 F NMR spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Mononuclear Four-Coordinate Bis-Fluoride Bis-NHC Complexes of Chromium(II), Iron(II), and Cobalt(II)

Acosta,

Belov,

Lamur

et al. 2023

Inorg. Chem.

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The reaction between silylamido complexes of Cr(II), Fe(II), and Co(II) and IMes•2HF salt in the presence of IMes (IMes = 1,3-dimesitylimidazol-2-ylidene) led to isolation of Cr(IMes) 2 F 2 (2-Cr), Fe(IMes) 2 F 2 (2-Fe), and Co(IMes) 2 F 2 (2-Co). X-ray structural studies revealed that 2-Cr adopts square planar geometry, while 2-Fe and 2-Co have distorted tetrahedral geometry. Magnetic susceptibility studies of 2-Cr, 2-Fe, and 2-Co were consistent with high-spin complexes, S = 2 for 2-Cr/ 2-Fe and S = 3/2 for 2-Co. We demonstrated that fluoride can be successfully exchanged for cyanide and azide using trimethylsilyl cyanide and trimethylsilyl azide (3-Fe and 4-Fe). DFT studies suggest that the preference of 2-Cr to adopt square planar geometry over tetrahedral is due to its d 4 metal center, where four electrons fill the lower-lying d-orbitals.

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