The Ce(III) hydrotris(3,5-dimethylpyrazolyl)borate complex [Ce(Tp
Me2)
2(κ
2-dmpz)] (
1) (Tp
Me2 = {HB(dmpz)
3}
−; dmpz = 3,5-dimethylpyrazolide) was isolated in fair yield from the reaction of [Ce(I)
3(THF)
4] with two equivalents of
[...] Read more.
The Ce(III) hydrotris(3,5-dimethylpyrazolyl)borate complex [Ce(Tp
Me2)
2(κ
2-dmpz)] (
1) (Tp
Me2 = {HB(dmpz)
3}
−; dmpz = 3,5-dimethylpyrazolide) was isolated in fair yield from the reaction of [Ce(I)
3(THF)
4] with two equivalents of [K(Tp
Me2)] via the facile decomposition of Tp
Me2. [Ce(Tp
Me2)
2(bipy)] (
2) was synthesized in poor yield by the “one-pot” reaction of [Ce(I)
3(THF)
4], bipy (bipy = 2,2′-bipyridine), KC
8 and two equivalents of [K(Tp
Me2)] in tetrahydrofuran (THF). The reaction of
2 with
N-methylmorpholine-
N-oxide produced the known decomposition product [Ce(Tp
Me2)(μ-BOp
Me2)]
2 (
3) (BOp
Me2 = {HBO(dmpz)
2}
2−) in poor yield, presumably by N–O and B–N bond cleavage of a reactive intermediate. The reaction of
2 with trimethylsilylazide gave [Ce(Tp
Me2)
2(N
3)] (
4) in poor yield; the fate of bipy and the trimethylsilyl group is unknown. Complexes
1–
4 were characterized by single crystal XRD, NMR and FTIR spectroscopy and elemental analysis. Complex
2 was additionally probed by UV/Vis/NIR and Electron Paramagnetic Resonance (EPR) spectroscopies, Cyclic Voltammetry (CV) and magnetometry, which together indicate a formal 4f
1 Ce(III) center coordinated by a bipy·
− radical anion in this system.
Full article
