Faculty of Chemistry and Pharmacy, Institute of General, Inorganic and Theoretical Chemistry, Leopold-Franzens-University Innsbruck, Innrain 80-82, 6020 Innsbruck, Austria.
Published: March 2020
AI Article Synopsis
Article Abstract
We present the synthesis of a series of new lanthanide(III) complexes supported by a monoanionic bidentate anilidophosphine ligand (-(2-(dipropylphosphanyl)-4-methylphenyl)-2,4,6-trimethylanilide, short PN). The work comprises the characterization of a variety of heteroleptic complexes containing either one or two PN ligands as well as a study on further functionalization possibilities. The new heteroleptic complexes cover selected examples over the whole lanthanide(III) series including lanthanum, cerium, neodymium, gadolinium, terbium, dysprosium, and lutetium. In case of the two diamagnetic metal cations lanthanum(III) and lutetium(III), we have furthermore studied the influence of the lanthanide ion (early vs. late) on the reactivity of these complexes. Thereby we found that the radius of the lanthanide ion has a major influence on the reactivity. Using sterically demanding, multidentate ligand systems, e.g., cyclopentadienide (Cp), we found that the lanthanum complex () reacts well to the corresponding cyclopentadienide complex, while for () no reaction was observed under any conditions tested. On the contrary, employing monodentate ligands such as mesitolate, thiomesitolate, 2,4,6-trimethylanilide or 2,4,6-trimethylphenylphosphide, results in the clean formation of the desired complexes for both lanthanum and lutetium. All complexes have been studied by various techniques, including multi nuclear NMR spectroscopy and X-ray crystallography. P NMR spectroscopy was furthermore used to evaluate the presence of open coordination sites on the complexes using coordinating and noncoordinating solvents, and as a probe for estimating the Ce-P distance in the corresponding complexes. Additionally, we present cyclic voltammetry (CV) data for (), (), () and () (with HMDS = hexamethyldisilazide, (MeSi)N) exploring the potential of the anilidophosphane ligand framework to stabilize a potential Ce(IV) ion.
Faculty of Chemistry and Pharmacy, Institute of General, Inorganic and Theoretical Chemistry, Leopold-Franzens-University Innsbruck, Innrain 80-82, 6020 Innsbruck, Austria.
We report a new synthetic entry to a series of -substituted anilidophosphine ligands (short HPN, R = pTol (), 3,5-dimethylphenyl (), 3,5-bis(trifluoromethyl)phenyl (), 2-methoxyphenyl (), diisopropylphenyl (), and adamantyl ()), allowing a detailed tuning of their steric (and electronic) properties. could be converted into their lithium salts , which are effective precursors for salt metathesis reactions. The new ligands are used for the synthesis of an array of lanthanide complexes using LaCl(THF) as a precursor.
University of Innsbruck, Center for Chemistry and Biomedicine, Department of General, Inorganic and Theoretical Chemistry, Innrain 80-82, 6020 Innsbruck, Austria.
Synthesis of a bulky anilidophosphine ligand (short PN) and its lanthanum complexes 1 and 3 is reported. When exposed to KPHMes, both complexes form the first example of a bis-phosphanido-phosphinidene complex 2. This complex undergoes Phospha-Wittig type reactions and its reactivity towards strong bases is further investigated.
Faculty of Chemistry and Pharmacy, Institute of General, Inorganic and Theoretical Chemistry, Leopold-Franzens-University Innsbruck, Innrain 80-82, 6020 Innsbruck, Austria.
We present the synthesis of a series of new lanthanide(III) complexes supported by a monoanionic bidentate anilidophosphine ligand (-(2-(dipropylphosphanyl)-4-methylphenyl)-2,4,6-trimethylanilide, short PN). The work comprises the characterization of a variety of heteroleptic complexes containing either one or two PN ligands as well as a study on further functionalization possibilities. The new heteroleptic complexes cover selected examples over the whole lanthanide(III) series including lanthanum, cerium, neodymium, gadolinium, terbium, dysprosium, and lutetium.
