Structural diversity in the series of lanthanide complexes [Ln(Ph3PO)n(NCS)3] (n = 3, 4)

Lawrence Chan; Simon A. Cotton; Joanna Dickson (nee Harris); Andrew W.G. Platt; Paul R. Raithby; Stefanie Schiffers; Alexander Tait; John E. Warren

doi:10.1016/j.poly.2022.115826

Structural diversity in the series of lanthanide complexes [Ln(Ph₃PO)_n(NCS)₃] (n = 3, 4)

Lawrence Chan, Simon A. Cotton, Joanna Dickson (nee Harris), Andrew W.G. Platt, Paul R. Raithby, Stefanie Schiffers, Alexander Tait, John E. Warren

Research output: Contribution to journal › Article › peer-review

Abstract

Two unique series of lanthanide complexes [Ln(Ph₃PO)₄(NCS)₃] (Ln = La-Tb, except Pm) and [Ln(Ph₃PO)₃(NCS)₃] (Ln = Sm-Lu, Y) have been structurally characterised. The isomorphous series [Ln(Ph₃PO)₄(NCS)₃] crystallises in the monoclinic centrosymmetric space group P2₁/c, and the metals display a capped octahedral coordination geometry. In contrast, the isomorphous series [Ln(Ph₃PO)₃(NCS)₃] (Ln = Sm-Lu, Y) crystallise in the non-centrosymmetric space group R3, with the metal displaying an octahedral coordination geometry; the fac-isomer being observed in all cases. Intriguingly, for the metals Sm-Tb both the seven and six coordinate complexes can be isolated from the respective synthetic routes suggesting a structural equilibrium in solution. An analysis of the distortions of the ligand polyhedron in the two series using the continuous shape measurement (CShMs) method suggests trends across the series relating to the fit of the ligands with the size of the lanthanide ions.

Original language	English
Article number	115826
Journal	Polyhedron
Volume	220
Early online date	4 Apr 2022
DOIs	https://doi.org/10.1016/j.poly.2022.115826
Publication status	Published - 1 Jul 2022

Keywords

Crystal structures
Lanthanide contraction
Lanthanides
Phosphine oxide
Thiocyanate

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10.1016/j.poly.2022.115826

https://researchportal.bath.ac.uk/en/publications/structural-diversity-in-the-series-of-lanthanide-complexes-lnphsuLicence: CC BY-NC-ND

Cite this

@article{e1d2bd1a406745d4a27a03f7b5376960,

title = "Structural diversity in the series of lanthanide complexes [Ln(Ph3PO)n(NCS)3] (n = 3, 4)",

abstract = "Two unique series of lanthanide complexes [Ln(Ph3PO)4(NCS)3] (Ln = La-Tb, except Pm) and [Ln(Ph3PO)3(NCS)3] (Ln = Sm-Lu, Y) have been structurally characterised. The isomorphous series [Ln(Ph3PO)4(NCS)3] crystallises in the monoclinic centrosymmetric space group P21/c, and the metals display a capped octahedral coordination geometry. In contrast, the isomorphous series [Ln(Ph3PO)3(NCS)3] (Ln = Sm-Lu, Y) crystallise in the non-centrosymmetric space group R3, with the metal displaying an octahedral coordination geometry; the fac-isomer being observed in all cases. Intriguingly, for the metals Sm-Tb both the seven and six coordinate complexes can be isolated from the respective synthetic routes suggesting a structural equilibrium in solution. An analysis of the distortions of the ligand polyhedron in the two series using the continuous shape measurement (CShMs) method suggests trends across the series relating to the fit of the ligands with the size of the lanthanide ions.",

keywords = "Crystal structures, Lanthanide contraction, Lanthanides, Phosphine oxide, Thiocyanate",

author = "Lawrence Chan and Cotton, {Simon A.} and {Dickson (nee Harris)}, Joanna and Platt, {Andrew W.G.} and Raithby, {Paul R.} and Stefanie Schiffers and Alexander Tait and Warren, {John E.}",

note = "Funding Information: We are grateful to the Engineering and Physical Sciences Research Council (UK) for a studentship to SS (EP/D072859/1) and for a Senior Fellowship to PRR (EP/D072859/1). Publisher Copyright: {\textcopyright} 2022 Elsevier Ltd",

year = "2022",

month = jul,

day = "1",

doi = "10.1016/j.poly.2022.115826",

language = "English",

volume = "220",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier BV",

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TY - JOUR

T1 - Structural diversity in the series of lanthanide complexes [Ln(Ph3PO)n(NCS)3] (n = 3, 4)

AU - Chan, Lawrence

AU - Cotton, Simon A.

AU - Dickson (nee Harris), Joanna

AU - Platt, Andrew W.G.

AU - Raithby, Paul R.

AU - Schiffers, Stefanie

AU - Tait, Alexander

AU - Warren, John E.

N1 - Funding Information: We are grateful to the Engineering and Physical Sciences Research Council (UK) for a studentship to SS (EP/D072859/1) and for a Senior Fellowship to PRR (EP/D072859/1). Publisher Copyright: © 2022 Elsevier Ltd

PY - 2022/7/1

Y1 - 2022/7/1

N2 - Two unique series of lanthanide complexes [Ln(Ph3PO)4(NCS)3] (Ln = La-Tb, except Pm) and [Ln(Ph3PO)3(NCS)3] (Ln = Sm-Lu, Y) have been structurally characterised. The isomorphous series [Ln(Ph3PO)4(NCS)3] crystallises in the monoclinic centrosymmetric space group P21/c, and the metals display a capped octahedral coordination geometry. In contrast, the isomorphous series [Ln(Ph3PO)3(NCS)3] (Ln = Sm-Lu, Y) crystallise in the non-centrosymmetric space group R3, with the metal displaying an octahedral coordination geometry; the fac-isomer being observed in all cases. Intriguingly, for the metals Sm-Tb both the seven and six coordinate complexes can be isolated from the respective synthetic routes suggesting a structural equilibrium in solution. An analysis of the distortions of the ligand polyhedron in the two series using the continuous shape measurement (CShMs) method suggests trends across the series relating to the fit of the ligands with the size of the lanthanide ions.

AB - Two unique series of lanthanide complexes [Ln(Ph3PO)4(NCS)3] (Ln = La-Tb, except Pm) and [Ln(Ph3PO)3(NCS)3] (Ln = Sm-Lu, Y) have been structurally characterised. The isomorphous series [Ln(Ph3PO)4(NCS)3] crystallises in the monoclinic centrosymmetric space group P21/c, and the metals display a capped octahedral coordination geometry. In contrast, the isomorphous series [Ln(Ph3PO)3(NCS)3] (Ln = Sm-Lu, Y) crystallise in the non-centrosymmetric space group R3, with the metal displaying an octahedral coordination geometry; the fac-isomer being observed in all cases. Intriguingly, for the metals Sm-Tb both the seven and six coordinate complexes can be isolated from the respective synthetic routes suggesting a structural equilibrium in solution. An analysis of the distortions of the ligand polyhedron in the two series using the continuous shape measurement (CShMs) method suggests trends across the series relating to the fit of the ligands with the size of the lanthanide ions.

KW - Crystal structures

KW - Lanthanide contraction

KW - Lanthanides

KW - Phosphine oxide

KW - Thiocyanate

U2 - 10.1016/j.poly.2022.115826

DO - 10.1016/j.poly.2022.115826

M3 - Article

AN - SCOPUS:85128216362

VL - 220

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

M1 - 115826

ER -