Structure and Stereochemistry of Adducts of Tris(dipivaloylmethanato)europium(III), Eu(dpm)3, with Some Dipolar Aprotic Unidentate O -Donors

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

Research output: Contribution to journalArticle

Abstract

Single crystal X-ray structural characterisations are reported for adducts of the form [(L-O)Eu(O,O′-dpm)3] obtained by the crystallisation of tris(dipivaloylmethanato)europium(iii) (dpm = [HC(C(tBu).CO)2]-) from an array of dipolar aprotic oxygen-donor solvents L (L = N-methylpyrrolidinone (nmp), trimethylphosphate, (MeO)3PO, (tmp), hexamethylphosphoramide (hmpa), dimethylacetamide (dma), dimethyl sulfoxide (dmso), and the bidentate octamethylpyrophosphoramide (ompa). In all adducts, the resulting arrays contain seven-coordinate metal atoms, which adopt two different isomeric forms of the mono-capped trigonal prismatic stereochemistry, the L = dma and dmso adducts corresponding to one type, nmp and tmp the other. The adduct formed with ompa behaves as a pair of discrete metal environments bridged by the O-ompa-O′ ligand, thus; [(dpm-O,O′)3Eu(O-ompa-O′)Eu(O,O′-dpm)3], and is found in two forms, one in which both Eu environments is of the tmp type, the other of the dmso/dma type. In the hmpa adduct, the asymmetric unit of the structure is a disordered composite of both types. In none of the adducts is there any further solvation beyond coordination of a single L.

Original languageEnglish
JournalAustralian Journal of Chemistry
DOIs
Publication statusE-pub ahead of print - 18 Jul 2019

Fingerprint

1-methyl-2-pyrrolidinone
Europium
Stereochemistry
Dimethyl Sulfoxide
Hempa
Metals
Solvation
Carbon Monoxide
Crystallization
Single crystals
Oxygen
Ligands
X rays
Atoms
Composite materials
trimethyl phosphate
dimethylacetamide

Cite this

@article{55aa05f7a6f0466b83ae468b09b46d59,
title = "Structure and Stereochemistry of Adducts of Tris(dipivaloylmethanato)europium(III), Eu(dpm)3, with Some Dipolar Aprotic Unidentate O -Donors",
abstract = "Single crystal X-ray structural characterisations are reported for adducts of the form [(L-O)Eu(O,O′-dpm)3] obtained by the crystallisation of tris(dipivaloylmethanato)europium(iii) (dpm = [HC(C(tBu).CO)2]-) from an array of dipolar aprotic oxygen-donor solvents L (L = N-methylpyrrolidinone (nmp), trimethylphosphate, (MeO)3PO, (tmp), hexamethylphosphoramide (hmpa), dimethylacetamide (dma), dimethyl sulfoxide (dmso), and the bidentate octamethylpyrophosphoramide (ompa). In all adducts, the resulting arrays contain seven-coordinate metal atoms, which adopt two different isomeric forms of the mono-capped trigonal prismatic stereochemistry, the L = dma and dmso adducts corresponding to one type, nmp and tmp the other. The adduct formed with ompa behaves as a pair of discrete metal environments bridged by the O-ompa-O′ ligand, thus; [(dpm-O,O′)3Eu(O-ompa-O′)Eu(O,O′-dpm)3], and is found in two forms, one in which both Eu environments is of the tmp type, the other of the dmso/dma type. In the hmpa adduct, the asymmetric unit of the structure is a disordered composite of both types. In none of the adducts is there any further solvation beyond coordination of a single L.",
author = "Chan, {Eric J.} and Harrowfield, {Jack M.} and Skelton, {Brian W.} and Sobolev, {Alexandre N.} and White, {Allan H.}",
year = "2019",
month = "7",
day = "18",
doi = "10.1071/CH19135",
language = "English",
journal = "Australian Journal of Chemistry:an international journal for chemical science",
issn = "0004-9425",
publisher = "CSIRO Publishing",

}

TY - JOUR

T1 - Structure and Stereochemistry of Adducts of Tris(dipivaloylmethanato)europium(III), Eu(dpm)3, with Some Dipolar Aprotic Unidentate O -Donors

AU - Chan, Eric J.

AU - Harrowfield, Jack M.

AU - Skelton, Brian W.

AU - Sobolev, Alexandre N.

AU - White, Allan H.

PY - 2019/7/18

Y1 - 2019/7/18

N2 - Single crystal X-ray structural characterisations are reported for adducts of the form [(L-O)Eu(O,O′-dpm)3] obtained by the crystallisation of tris(dipivaloylmethanato)europium(iii) (dpm = [HC(C(tBu).CO)2]-) from an array of dipolar aprotic oxygen-donor solvents L (L = N-methylpyrrolidinone (nmp), trimethylphosphate, (MeO)3PO, (tmp), hexamethylphosphoramide (hmpa), dimethylacetamide (dma), dimethyl sulfoxide (dmso), and the bidentate octamethylpyrophosphoramide (ompa). In all adducts, the resulting arrays contain seven-coordinate metal atoms, which adopt two different isomeric forms of the mono-capped trigonal prismatic stereochemistry, the L = dma and dmso adducts corresponding to one type, nmp and tmp the other. The adduct formed with ompa behaves as a pair of discrete metal environments bridged by the O-ompa-O′ ligand, thus; [(dpm-O,O′)3Eu(O-ompa-O′)Eu(O,O′-dpm)3], and is found in two forms, one in which both Eu environments is of the tmp type, the other of the dmso/dma type. In the hmpa adduct, the asymmetric unit of the structure is a disordered composite of both types. In none of the adducts is there any further solvation beyond coordination of a single L.

AB - Single crystal X-ray structural characterisations are reported for adducts of the form [(L-O)Eu(O,O′-dpm)3] obtained by the crystallisation of tris(dipivaloylmethanato)europium(iii) (dpm = [HC(C(tBu).CO)2]-) from an array of dipolar aprotic oxygen-donor solvents L (L = N-methylpyrrolidinone (nmp), trimethylphosphate, (MeO)3PO, (tmp), hexamethylphosphoramide (hmpa), dimethylacetamide (dma), dimethyl sulfoxide (dmso), and the bidentate octamethylpyrophosphoramide (ompa). In all adducts, the resulting arrays contain seven-coordinate metal atoms, which adopt two different isomeric forms of the mono-capped trigonal prismatic stereochemistry, the L = dma and dmso adducts corresponding to one type, nmp and tmp the other. The adduct formed with ompa behaves as a pair of discrete metal environments bridged by the O-ompa-O′ ligand, thus; [(dpm-O,O′)3Eu(O-ompa-O′)Eu(O,O′-dpm)3], and is found in two forms, one in which both Eu environments is of the tmp type, the other of the dmso/dma type. In the hmpa adduct, the asymmetric unit of the structure is a disordered composite of both types. In none of the adducts is there any further solvation beyond coordination of a single L.

UR - http://www.scopus.com/inward/record.url?scp=85069789575&partnerID=8YFLogxK

U2 - 10.1071/CH19135

DO - 10.1071/CH19135

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 -