Homoleptic rare earth dipyridylamides [Ln2(N(NC5H4)2)6], Ln = Ce, Nd, Sm, Ho, Er, Tm, Yb, and Sc: metal oxidation by the amine melt and in 1,2,3,4-tetrahydroquinoline with the focus of different metal activation by amalgams, liquid ammonia, and microwaves

Inorganic Chemistry
Klaus Müller-Buschbaum, Catharina C Quitmann

Abstract

Homoleptic dimeric dipyridylamide complexes of the rare earth elements are obtained by solvent-free oxidation reactions of the metals with melts of 2,2'-dipyridylamine. As the thermal stabilities of the ligand as well as the amide complexes are limiting factors in these high-temperature syntheses, several different metal activation procedures have been investigated: the formation of Ln amalgams and dissolution of the metals in liquid ammonia as well as coupling to microwaves. For comparison with a solvent that shows low solubility of the metals and products, reactions in 1,2,3,4-tetrahydroquinoline were also carried out. For all lanthanides and group 3 metals used homoleptic dimers of the formula [Ln(2)(Dpa)(6)], Ln = Ce (1), Nd (2), Sm (3), Ho (4), Er (5), Tm (6), Yb (7), and Sc (8) and Dpa- = (C5H4N)2N-, were obtained, all containing trivalent rare earth ions with a distorted square antiprismatic nitrogen coordination. Due to the large differences in the ionic radii of the metal ions, two different structure types are found that crystallize in the space groups P2(1)/c and P2(1)/n with the border of the two types being between Tm and Yb. The orientations of two 1,3/1,3-double chelating and linking dipyridylamide ligands (Dpa(-...Continue Reading

Citations

Feb 5, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Jingjing LiangDingxian Jia
Mar 18, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Javier CepedaAntonio Luque
Oct 23, 2010·Chemical Communications : Chem Comm·Alexander ZurawskiKlaus Müller-Buschbaum
Dec 22, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Christoph J HöllerKlaus Müller-Buschbaum
Aug 1, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Guang-Cai ZongShi-Kao Shi
Oct 17, 2018·Chemistry : a European Journal·Zhifang GuoPeter Courtney Junk
Nov 20, 2009·Inorganic Chemistry·Michael NippeJohn F Berry
Oct 7, 2021·Chemistry : a European Journal·Heba YoussefKlaus Müller-Buschbaum

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