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 language | English |
|---|---|
| Journal | Australian Journal of Chemistry |
| DOIs | |
| Publication status | Published - 1 Jan 2019 |
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Structural Systematics of Lanthanide(III) Picrate Solvates : Adducts of the Carboxamide Ligands Dimethylacetamide and N-Methylpyrrolidinone. / Chan, Eric J.; Harrowfield, Jack M.; Skelton, Brian W.; Sobolev, Alexandre N.; White, Allan H.
In: Australian Journal of Chemistry, 01.01.2019.Research output: Contribution to journal › Article
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 -