[Yb₃N(dpa)₆][Yb(dpa)₃]: A Molecular Nitride of a Rare‐Earth Metal with a Yb₃N Unit

Abstract

Centered by a nitride ion: The oxidation of ytterbium with 2,2′‐dipyridylamine in liquid ammonia at low temperatures leads to the novel compound [Yb3N(dpa)6][Yb(dpa)3], which is unique among homoleptic dipyridylamides of the rare‐earth metals. The complete deprotonation of NH3 provides the first molecular nitride of a rare‐earth metal with a Yb3N unit (see picture; C blue, N green, Yb silver).

Rare Earth Starting Materials and Methodologies for Synthetic Chemistry

“…In the case of the reaction between Yb and carbazole (C 12 H 8 NH, CarbH), N- phenylpiperazine (Phpip) was added to aid crystallization of the target complex [Yb­(Carb) 2 (NH 3 ) 4 ] ( 12 , Carb = carbazolide, {C 12 H 8 N} − ), though this product cannot be separated from cocrystallized CarbH·Phpip . It is also noteworthy that Müller-Buschbaum and co-workers extended this work to various divalent and trivalent REs by reacting metal powders with amines, either directly or in the presence of trace amounts of Hg under solvothermal conditions ( vide infra , sections and ). , Remarkably, the use of ammoniacal Yb solutions in the presence of 2,2′-dipyridylamine afforded the isolation of the first RE molecular nitride [Yb 3 N­(dpa) 6 ]­[Yb­(dpa) 3 ] ( 15 , dpa = 2,2′-dipyridylamide, {(C 6 H 4 N) 2 N} − ) …”

“…77,99 Remarkably, the use of ammoniacal Yb solutions in the presence of 2,2′-dipyridylamine afforded the isolation of the first RE molecular nitride [Yb 3 N(dpa) 6 ][Yb(dpa) 3 ] (15, dpa = 2,2′dipyridylamide, {(C 6 H 4 N) 2 N} − ). 100…”

Coordination Chemistry of 2,2’-Dipyridylamine: The Gift That Keeps on Giving

“…[32][33][34][35] Mϋller-Buschbaum and Quitmann have synthesized a series of Ln 2 (dpa) 6 (Ln = La, Ce, Nd, Sm, Gd, Ho, Er, Tm, Yb, and Sc) compounds by stoichiometric redox melt reactions between the lanthanide metal (activated by a mercury amalgam) and dpaH, equation 3. [32,34] The rare earth ions are trivalent in these structures and adopt a distorted square antiprismatic configuration.…”

“…[35] Quitmann and Mϋller-Buschbaum have also synthesized another unique rare earth metal dpa compound, namely, [Yb 3 N(dpa) 6 ]•[Yb(dpa) 3 ], Figure 12. [33] Substantial effort has been put forth to study homoleptic dinuclear transition metal dpa complexes of the form M 2 (dpa) 4 , M 2 = V 2 , [36] Cr 2 , [37,38] Mo 2 , [39] MoW, [40] W 2 , [41] and Rh 2 . [42] These compounds feature four dpa ligands coordinated around the metal centers to form a paddlewheel type structure, Figure 13; however, the chelation mode of dpa in the V 2 complex is different than for the group VI metals, which is also different than observed for the Rh 2 complex.…”

“…Molecular structure of [Yb 3 N(dpa) 6 ]. [33] Figure 17. X-ray crystal structure of Mo 2 Ru(dpa) 4 Cl.…”