Bulky ortho 3-methoxy groups on N[sub 4]O[sub 3] amine phenol ligands producing six-coordinate bis(ligand)lanthanide complex cations [Ln(H[sub 3]L)[sub 2]][sup 3+] (Ln = Pr, Gd; H[sub 3]L = tris (((2-hydroxy-3-methoxybenzyl)amino)ethyl)amine)

Journal Article · Wed Jun 09 00:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00064a031· OSTI ID:5782404

Liu, S; Yang, L W; Rettig, S J; Orvig, C ^[1]

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1. Univ. of British Columbia, Vancouver (Canada)

The synthesis and characterization of an N[sub 4]O[sub 3] amine phenol (tris(((2-hydroxy-3-methoxybenzyl)amino)ethyl)amine, H[sub 3]L4) and its lanthanide complexes [Ln(H[sub 3]L4)(NO[sub 3])[sub 3]] (Ln = Pr, Nd) and [Ln(H[sub 3]L4)[sub 2]](NO[sub 3])[sub 3] (Ln = Pr, Nd, Gd, Yb) are reported. The N[sub 4]O[sub 3] amine phenol ligand is the KBH[sub 4] reduction product of the Schiff base derived from the reaction of tris(2-aminoethyl)amine (tren) and 3 equiv of o-vanillin. The reactions of lanthanide nitrates with 1 equiv of H[sub 3]L4 produce nine-coordinate type II complexes, [Ln(H[sub 3]L4)(NO[sub 3]][sub 3] (Ln = Gd, Yb). The latter were prepared from the reactions of lanthanide nitrates with 2 equiv of H[sub 3]L4) in the presence of sodium hydroxide. The X-ray crystal structures of [Ln(H[sub 3]L4)[sub 2]] (NO[sub 3])[sub 3][center dot]xH[sub 2]O[center dot]yMeOH (Ln = Pr, x = 5.56, y = 0.44; Ln = Gd, x = 5.96, y = 0.66) have been determined. Crystals of [Ln(H[sub 3]L4)[sub 2]](NO[sub 3])[sub 3][center dot]xH[sub 2]O[center dot]yMeOH (Ln = Pr, x = 5.56, y = 0.44; Ln = Gd, x = 5.96, y = 0.66) are isomorphous, crystallizing in a monoclinic space group. The structures were solved by the Patterson method and were refined by full-matrix least-squares procedures to R = 0.033 [0.033] and R[sub w] = 0.040 [0.036] for 5032 [5867] reflections with I [ge] 3[sigma](I), respectively. In both complexes, the three phenolate O atoms of each of the two tridentate amine phenol ligands coordinate to the metal ions in a slightly distorted octahedral geometry while the secondary amine N atoms are protonated and uncoordinated. The effects of bulky 3-methoxy groups of the phenyl rings on the coordinating behavior toward lanthanide metals are discussed.

• OSTI ID: 5782404
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:12; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
GADOLINIUM COMPLEXES
CHEMICAL PREPARATION
PRASEODYMIUM COMPLEXES
CATIONS
CRYSTAL STRUCTURE
LATTICE PARAMETERS
LIGANDS
MOLECULAR STRUCTURE
MONOCLINIC LATTICES
PATTERSON METHOD
REDUCTION
STOICHIOMETRY
X-RAY DIFFRACTION
CALCULATION METHODS
CHARGED PARTICLES
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
DIFFRACTION
IONS
RARE EARTH COMPLEXES
SCATTERING
SYNTHESIS
400201* - Chemical & Physicochemical Properties