Structural Systematics of Lanthanide(iii) Picrate Solvates: Molecular, Mononuclear Ln(pic)3(trimethylphosphate)3 Arrays

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

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Abstract

Adducts of the form Ln(pic)3(tmp)3 (Ln = lanthanide(iii); pic = picrate = 2,4,6-trinitrophenoxide; tmp = trimethylphosphate, (MeO)3PO) have been prepared for extremal Ln = La, Lu and some intermediate members, also Y, and characterised by single crystal X-ray structure determinations as unsolvated, mononuclear, molecular species. The lanthanide atom has nine-coordinate, tri-capped trigonal prismatic stereochemistry in all cases, the picrate components behaving as O,O′-bidentate ligands chelating through the phenoxy- and an adjacent O-nitro oxygen atom, thus: [Ln(tmp-O)3(pic-O,O′)3]. Two isomeric forms are found, one mer in which the three unidentate tmp-O ligands coordinate in cis-sites spanning the upper and lower triangles and a capping site of the coordination sphere, and fac, in which all three unidentate ligands occupy the mutually cis-sites of one triangular face. The mer isomer has been described as an isomorphous series in a monoclinic P21/c, Z 4, form, for Ln = La, Ce, Pr, Nd, Sm, Gd, Lu, and Y, presumptively accessible for the full gamut of Ln. The fac-isomer also crystallises in a monoclinic P21/c form, Z 8, two independent molecules of similar stereochemistry here comprising the asymmetric unit and described for Ln = Eu, Lu(isomorphous); it has also been described in a triclinic PCH19176-IE1.gif, Z 2 form for Ln = La.

Original languageEnglish
JournalAustralian Journal of Chemistry
DOIs
Publication statusE-pub ahead of print - 3 Jul 2019

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Lanthanoid Series Elements
Stereochemistry
Ligands
Isomers
Atoms
Chelation
Single crystals
Oxygen
X rays
Molecules
trimethyl phosphate
picric acid

Cite this

@article{ac0af8c54e104a77b44391c37546f340,
title = "Structural Systematics of Lanthanide(iii) Picrate Solvates: Molecular, Mononuclear Ln(pic)3(trimethylphosphate)3 Arrays",
abstract = "Adducts of the form Ln(pic)3(tmp)3 (Ln = lanthanide(iii); pic = picrate = 2,4,6-trinitrophenoxide; tmp = trimethylphosphate, (MeO)3PO) have been prepared for extremal Ln = La, Lu and some intermediate members, also Y, and characterised by single crystal X-ray structure determinations as unsolvated, mononuclear, molecular species. The lanthanide atom has nine-coordinate, tri-capped trigonal prismatic stereochemistry in all cases, the picrate components behaving as O,O′-bidentate ligands chelating through the phenoxy- and an adjacent O-nitro oxygen atom, thus: [Ln(tmp-O)3(pic-O,O′)3]. Two isomeric forms are found, one mer in which the three unidentate tmp-O ligands coordinate in cis-sites spanning the upper and lower triangles and a capping site of the coordination sphere, and fac, in which all three unidentate ligands occupy the mutually cis-sites of one triangular face. The mer isomer has been described as an isomorphous series in a monoclinic P21/c, Z 4, form, for Ln = La, Ce, Pr, Nd, Sm, Gd, Lu, and Y, presumptively accessible for the full gamut of Ln. The fac-isomer also crystallises in a monoclinic P21/c form, Z 8, two independent molecules of similar stereochemistry here comprising the asymmetric unit and described for Ln = Eu, Lu(isomorphous); it has also been described in a triclinic PCH19176-IE1.gif, Z 2 form for Ln = La.",
author = "Chan, {Eric J.} and Harrowfield, {Jack M.} and Skelton, {Brian W.} and Sobolev, {Alexandre N.} and White, {Allan H.}",
year = "2019",
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doi = "10.1071/CH19176",
language = "English",
journal = "Australian Journal of Chemistry:an international journal for chemical science",
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T1 - Structural Systematics of Lanthanide(iii) Picrate Solvates

T2 - Molecular, Mononuclear Ln(pic)3(trimethylphosphate)3 Arrays

AU - Chan, Eric J.

AU - Harrowfield, Jack M.

AU - Skelton, Brian W.

AU - Sobolev, Alexandre N.

AU - White, Allan H.

PY - 2019/7/3

Y1 - 2019/7/3

N2 - Adducts of the form Ln(pic)3(tmp)3 (Ln = lanthanide(iii); pic = picrate = 2,4,6-trinitrophenoxide; tmp = trimethylphosphate, (MeO)3PO) have been prepared for extremal Ln = La, Lu and some intermediate members, also Y, and characterised by single crystal X-ray structure determinations as unsolvated, mononuclear, molecular species. The lanthanide atom has nine-coordinate, tri-capped trigonal prismatic stereochemistry in all cases, the picrate components behaving as O,O′-bidentate ligands chelating through the phenoxy- and an adjacent O-nitro oxygen atom, thus: [Ln(tmp-O)3(pic-O,O′)3]. Two isomeric forms are found, one mer in which the three unidentate tmp-O ligands coordinate in cis-sites spanning the upper and lower triangles and a capping site of the coordination sphere, and fac, in which all three unidentate ligands occupy the mutually cis-sites of one triangular face. The mer isomer has been described as an isomorphous series in a monoclinic P21/c, Z 4, form, for Ln = La, Ce, Pr, Nd, Sm, Gd, Lu, and Y, presumptively accessible for the full gamut of Ln. The fac-isomer also crystallises in a monoclinic P21/c form, Z 8, two independent molecules of similar stereochemistry here comprising the asymmetric unit and described for Ln = Eu, Lu(isomorphous); it has also been described in a triclinic PCH19176-IE1.gif, Z 2 form for Ln = La.

AB - Adducts of the form Ln(pic)3(tmp)3 (Ln = lanthanide(iii); pic = picrate = 2,4,6-trinitrophenoxide; tmp = trimethylphosphate, (MeO)3PO) have been prepared for extremal Ln = La, Lu and some intermediate members, also Y, and characterised by single crystal X-ray structure determinations as unsolvated, mononuclear, molecular species. The lanthanide atom has nine-coordinate, tri-capped trigonal prismatic stereochemistry in all cases, the picrate components behaving as O,O′-bidentate ligands chelating through the phenoxy- and an adjacent O-nitro oxygen atom, thus: [Ln(tmp-O)3(pic-O,O′)3]. Two isomeric forms are found, one mer in which the three unidentate tmp-O ligands coordinate in cis-sites spanning the upper and lower triangles and a capping site of the coordination sphere, and fac, in which all three unidentate ligands occupy the mutually cis-sites of one triangular face. The mer isomer has been described as an isomorphous series in a monoclinic P21/c, Z 4, form, for Ln = La, Ce, Pr, Nd, Sm, Gd, Lu, and Y, presumptively accessible for the full gamut of Ln. The fac-isomer also crystallises in a monoclinic P21/c form, Z 8, two independent molecules of similar stereochemistry here comprising the asymmetric unit and described for Ln = Eu, Lu(isomorphous); it has also been described in a triclinic PCH19176-IE1.gif, Z 2 form for Ln = La.

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U2 - 10.1071/CH19176

DO - 10.1071/CH19176

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

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