Synthesis and Characterization of Paramagnetic Lanthanide Benzyl Complexes

Abstract

The organometallic chemistry of paramagnetic lanthanides (Ln, from Ce to Yb) is far less developed compared to that of their diamagnetic counterparts (Sc, Y, La, and Lu). Lack of available starting materials and characterization methods are the major obstacles. Herein we report the synthesis and characterization of trisbenzyl complexes of neodymium, gadolinium, holmium, and erbium. In addition, we introduce a direct procedure for the synthesis of lanthanide benzyl and iodide complexes supported by a ferrocene diamide ligand starting from the corresponding oxides. All newly synthesized compounds were characterized by X-ray crystallography, 1 H NMR spectroscopy (except for gadolinium compounds, which were NMR silent), and elemental analysis.

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2013

“…However, the rate efficiencies vary dramatically along the period 0.73 (Sc), 0.91 (Ti), and 0.028 (V) in agreement with the experimental observation [2]. A detailed computational study on the equilibrium geometries, stability and vibrational frequencies of a series of Sc(CO) n (n = 1-7), Sc(CO) 7 − and Sc(CO) 6 3− has been reported using density functional theory functionals and the coupled cluster (single-point) method with 6-311 + G(3df) basis set. It was shown that the obtained sequential and average CO binding energies of Sc(CO) n (n = 4-7), Sc(CO) 7 − and Sc(CO) 6 3− are comparable to those of experimentally known species, i.e., smaller scandium carbonyls (n < 3) and the analog Ti(CO) 7 + .…”

Tetraanionic Biphenyl Lanthanide Complexes as Single-Molecule Magnets

“…Overall yield from Dy2O3: 77.0%. The empirical formula DyBr3(THF)3.5 was determined by considering the mass change upon treatment with THF 22 and was used as such in subsequent procedures.…”

P4 Activation by Lanthanum and Lutetium Naphthalene Complexes Supported by a Ferrocene Diamide Ligand

“…Colorless or white crystals of P4 were obtained at -35 °C and stored in a -35°C freezer prior to use. (NN fc )LaI(THF) [34] and (NN fc )LuI(THF)2 [35] were prepared following literature protocols. Nuclear magnetic resonance (NMR) spectra were recorded on Bruker AV300, Bruker DRX500, Bruker AV500 (work supported by the NSF grants CHE-1048804), or Bruker AV600 spectrometers at 25 °C in C6D6 or C7D8 unless otherwise specified.…”