Structural Systematics of Lanthanide(III) Picrate Solvates: Adducts of the Carboxamide Ligands Dimethylacetamide and N-Methylpyrrolidinone

Eric J. Chan, Jack M. Harrowfield, Brian W. Skelton, Alexandre N. Sobolev, Allan H. White

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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.

Original languageEnglish
JournalAustralian Journal of Chemistry
DOIs
Publication statusPublished - 1 Jan 2019

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1-methyl-2-pyrrolidinone
Lanthanoid Series Elements
Hempa
Ligands
Dimethyl Sulfoxide
Picrates
Alcohols
Stereoisomerism
Chelation
Polymorphism
Chemical analysis
Stoichiometry
Ethanol
Geometry
picric acid
dimethylacetamide

Cite this

@article{6d8fa9c7b49f433196e5dd56eb89421a,
title = "Structural Systematics of Lanthanide(III) Picrate Solvates: Adducts of the Carboxamide Ligands Dimethylacetamide and N-Methylpyrrolidinone",
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.",
author = "Chan, {Eric J.} and Harrowfield, {Jack M.} and Skelton, {Brian W.} and Sobolev, {Alexandre N.} and White, {Allan H.}",
year = "2019",
month = "1",
day = "1",
doi = "10.1071/CH19275",
language = "English",
journal = "Australian Journal of Chemistry:an international journal for chemical science",
issn = "0004-9425",
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TY - JOUR

T1 - Structural Systematics of Lanthanide(III) Picrate Solvates

T2 - Adducts of the Carboxamide Ligands Dimethylacetamide and N-Methylpyrrolidinone

AU - Chan, Eric J.

AU - Harrowfield, Jack M.

AU - Skelton, Brian W.

AU - Sobolev, Alexandre N.

AU - White, Allan H.

PY - 2019/1/1

Y1 - 2019/1/1

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85073693270&partnerID=8YFLogxK

U2 - 10.1071/CH19275

DO - 10.1071/CH19275

M3 - Article

JO - Australian Journal of Chemistry:an international journal for chemical science

JF - Australian Journal of Chemistry:an international journal for chemical science

SN - 0004-9425

ER -