Structural Systematics of Lanthanide(iii) Picrate Solvates: Adducts of the Carboxamide Ligands Dimethylacetamide and N-Methylpyrrolidinone
Eric J. Chan A , Jack M. Harrowfield A B D , Brian W. Skelton A , Alexandre N. Sobolev A and Allan H. White A CA School of Molecular Sciences, M310, University of Western Australia, 35 Stirling Hwy, Perth, WA 6009, Australia.
B Current address: Institut de Science et d’Ingénierie Supramoléculaires, Université de Strasbourg, 8, allée Gaspard Monge, Strasbourg, 67083, France.
C Deceased.
D Corresponding author. Email: harrowfield@unistra.fr
Australian Journal of Chemistry 73(6) 488-496 https://doi.org/10.1071/CH19275
Submitted: 17 June 2019 Accepted: 27 August 2019 Published: 10 October 2019
Abstract
The carboxamide-O donor ligands dimethylacetamide (dma) and N-methylpyrrolidinone (nmp) form complexes of lanthanide picrates, Ln(pic)3, of stoichiometry Ln(pic)3(carboxamide)3 in a remarkable variety of phases. Complexes [Ln(pic)3(dma)3], Ln = La, Ce, Nd, Sm, Gd, Yb, Lu, and Y, adopt the 9-coordinate molecular form of tricapped trigonal-prismatic coordination geometry seen to predominate, as two stereoisomers, in related species involving dimethylsulfoxide (dmso), trimethylphosphate (tmp), and hexamethylphosphoramide (hmpa) but as four different phases (depending on Ln), none of which is the same as for the previously known La complex. For Ln = Pr, 9-coordinate species of composition [Pr(pic)3(dma)2(alcohol)] (alcohol = ethanol and propan-2-ol) have been characterised and a low quality determination indicates that a similar species (with propan-2-ol) is formed by Y. For nmp, the composition [Ln(pic)3(nmp)3] is maintained across the series for Ln = La, Ce, Pr, Nd, Gd, Er, Tm, Yb, and Lu but 9-coordination is not for Ln = Er, Tm, Yb, and Lu. A decreased coordination there is a result of one or two picrate ligands acting as phenoxide-O donors only, a marked contrast with the analogous Ln(pic)3 complexes with dmso, tmp, hmpa, and dma, where picrate chelation is universal, but with some parallel to related ScIII complexes. Several polymorph pairs can be identified among the nmp complexes.
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