Imidobis(tetraphenylphosphinato)lanthanoid(III) complexes: Synthesis by oxidative protolysis, and redox transmetallation/protolysis, structural studies and Hirshfeld surface analysis

Shalini Rangarajan; Owen A. Beaumont; Maravanji S. Balakrishna; Glen B. Deacon; Victoria L. Blair

doi:10.1016/j.ica.2024.122385

Imidobis(tetraphenylphosphinato)lanthanoid(III) complexes: Synthesis by oxidative protolysis, and redox transmetallation/protolysis, structural studies and Hirshfeld surface analysis

Shalini Rangarajan, Owen A. Beaumont, Maravanji S. Balakrishna, Glen B. Deacon, Victoria L. Blair

School of Chemistry

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

2 Citations (Scopus)

Abstract

Redox protolysis of [YbCp₂(dme)] (dme = 1,2-dimethoxyethane) by imidotetraphenyldiphosphinate, ({Ph₂PO}₂NH) LH yields [YbCp{(Ph₂PO)₂N}₂}(MeCN)] 1 and [Yb{(Ph₂PO)₂N}₃] 2 with the last also obtained by oxidative protolysis of Yb(C₆F₅)₂. The complexes [Ln{(Ph₂PO)₂N}₃] ((Ln = Yb 2, Er 3, Gd 4), [Sm{(Ph₂PO)₂N}₃(MeCN)₃] 5 and [Nd{(Ph₂ PO)₂N}₃] 6 have all been prepared by redox transmetallation/protolysis reactions between Yb, Er, Gd, Sm or Nd metals, bispentafluorophenylmercury and proligand LH. Complex 1 is formally eight coordinate with an acetonitrile, cyclopentadienyl (Cp) and two chelating O,O′-(Ph₂PO)₂N ligands, with the MeCN trans to the Cp ring. Complexes 2 and 4·C₇H₈ are six coordinate monomers with three chelating O,O′ diphosphinate ligands. By contrast 5 is a highly symmetrical nine-coordinate monomer with three acetonitrile and three chelating O,O′-L ligands. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint plots (2D-FP) were quantified for different intermolecular interactions in complexes 2 and 4.

Original language	English
Article number	122385
Number of pages	9
Journal	Inorganica Chimica Acta
Volume	574
DOIs	https://doi.org/10.1016/j.ica.2024.122385
Publication status	Published - 1 Jan 2025

Keywords

Imidodiphosphinate
Lanthanoid
Redox protolysis
Redox transmetallation/protolysis
Structural analysis

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10.1016/j.ica.2024.122385Licence: CC BY

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@article{bc105e39354641ad8da008a54bc07179,

title = "Imidobis(tetraphenylphosphinato)lanthanoid(III) complexes: Synthesis by oxidative protolysis, and redox transmetallation/protolysis, structural studies and Hirshfeld surface analysis",

abstract = "Redox protolysis of [YbCp2(dme)] (dme = 1,2-dimethoxyethane) by imidotetraphenyldiphosphinate, (\{Ph2PO\}2NH) LH yields [YbCp\{(Ph2PO)2N\}2\}(MeCN)] 1 and [Yb\{(Ph2PO)2N\}3] 2 with the last also obtained by oxidative protolysis of Yb(C6F5)2. The complexes [Ln\{(Ph2PO)2N\}3] ((Ln = Yb 2, Er 3, Gd 4), [Sm\{(Ph2PO)2N\}3(MeCN)3] 5 and [Nd\{(Ph2 PO)2N\}3] 6 have all been prepared by redox transmetallation/protolysis reactions between Yb, Er, Gd, Sm or Nd metals, bispentafluorophenylmercury and proligand LH. Complex 1 is formally eight coordinate with an acetonitrile, cyclopentadienyl (Cp) and two chelating O,O′-(Ph2PO)2N ligands, with the MeCN trans to the Cp ring. Complexes 2 and 4·C7H8 are six coordinate monomers with three chelating O,O′ diphosphinate ligands. By contrast 5 is a highly symmetrical nine-coordinate monomer with three acetonitrile and three chelating O,O′-L ligands. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint plots (2D-FP) were quantified for different intermolecular interactions in complexes 2 and 4.",

keywords = "Imidodiphosphinate, Lanthanoid, Redox protolysis, Redox transmetallation/protolysis, Structural analysis",

author = "Shalini Rangarajan and Beaumont, \{Owen A.\} and Balakrishna, \{Maravanji S.\} and Deacon, \{Glen B.\} and Blair, \{Victoria L.\}",

note = "Publisher Copyright: {\textcopyright} 2024 The Author(s)",

year = "2025",

month = jan,

day = "1",

doi = "10.1016/j.ica.2024.122385",

language = "English",

volume = "574",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier",

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Imidobis(tetraphenylphosphinato)lanthanoid(III) complexes: Synthesis by oxidative protolysis, and redox transmetallation/protolysis, structural studies and Hirshfeld surface analysis. / Rangarajan, Shalini; Beaumont, Owen A.; Balakrishna, Maravanji S. et al.
In: Inorganica Chimica Acta, Vol. 574, 122385, 01.01.2025.

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

TY - JOUR

T1 - Imidobis(tetraphenylphosphinato)lanthanoid(III) complexes

T2 - Synthesis by oxidative protolysis, and redox transmetallation/protolysis, structural studies and Hirshfeld surface analysis

AU - Rangarajan, Shalini

AU - Beaumont, Owen A.

AU - Balakrishna, Maravanji S.

AU - Deacon, Glen B.

AU - Blair, Victoria L.

PY - 2025/1/1

Y1 - 2025/1/1

N2 - Redox protolysis of [YbCp2(dme)] (dme = 1,2-dimethoxyethane) by imidotetraphenyldiphosphinate, ({Ph2PO}2NH) LH yields [YbCp{(Ph2PO)2N}2}(MeCN)] 1 and [Yb{(Ph2PO)2N}3] 2 with the last also obtained by oxidative protolysis of Yb(C6F5)2. The complexes [Ln{(Ph2PO)2N}3] ((Ln = Yb 2, Er 3, Gd 4), [Sm{(Ph2PO)2N}3(MeCN)3] 5 and [Nd{(Ph2 PO)2N}3] 6 have all been prepared by redox transmetallation/protolysis reactions between Yb, Er, Gd, Sm or Nd metals, bispentafluorophenylmercury and proligand LH. Complex 1 is formally eight coordinate with an acetonitrile, cyclopentadienyl (Cp) and two chelating O,O′-(Ph2PO)2N ligands, with the MeCN trans to the Cp ring. Complexes 2 and 4·C7H8 are six coordinate monomers with three chelating O,O′ diphosphinate ligands. By contrast 5 is a highly symmetrical nine-coordinate monomer with three acetonitrile and three chelating O,O′-L ligands. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint plots (2D-FP) were quantified for different intermolecular interactions in complexes 2 and 4.

AB - Redox protolysis of [YbCp2(dme)] (dme = 1,2-dimethoxyethane) by imidotetraphenyldiphosphinate, ({Ph2PO}2NH) LH yields [YbCp{(Ph2PO)2N}2}(MeCN)] 1 and [Yb{(Ph2PO)2N}3] 2 with the last also obtained by oxidative protolysis of Yb(C6F5)2. The complexes [Ln{(Ph2PO)2N}3] ((Ln = Yb 2, Er 3, Gd 4), [Sm{(Ph2PO)2N}3(MeCN)3] 5 and [Nd{(Ph2 PO)2N}3] 6 have all been prepared by redox transmetallation/protolysis reactions between Yb, Er, Gd, Sm or Nd metals, bispentafluorophenylmercury and proligand LH. Complex 1 is formally eight coordinate with an acetonitrile, cyclopentadienyl (Cp) and two chelating O,O′-(Ph2PO)2N ligands, with the MeCN trans to the Cp ring. Complexes 2 and 4·C7H8 are six coordinate monomers with three chelating O,O′ diphosphinate ligands. By contrast 5 is a highly symmetrical nine-coordinate monomer with three acetonitrile and three chelating O,O′-L ligands. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint plots (2D-FP) were quantified for different intermolecular interactions in complexes 2 and 4.

KW - Imidodiphosphinate

KW - Lanthanoid

KW - Redox protolysis

KW - Redox transmetallation/protolysis

KW - Structural analysis

UR - https://www.scopus.com/pages/publications/85204936694

U2 - 10.1016/j.ica.2024.122385

DO - 10.1016/j.ica.2024.122385

M3 - Article

AN - SCOPUS:85204936694

SN - 0020-1693

VL - 574

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

M1 - 122385

ER -

Imidobis(tetraphenylphosphinato)lanthanoid(III) complexes: Synthesis by oxidative protolysis, and redox transmetallation/protolysis, structural studies and Hirshfeld surface analysis

Abstract

Keywords

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Advancing the chemistry of rare earths - an Australian resource

CTREC: Challenging targets in rare earth metal-organic chemistry

Australian Synchrotron

Cite this

Imidobis(tetraphenylphosphinato)lanthanoid(III) complexes: Synthesis by oxidative protolysis, and redox transmetallation/protolysis, structural studies and Hirshfeld surface analysis

Abstract

Keywords

Access to Document

Other files and links

Projects

Advancing the chemistry of rare earths - an Australian resource

CTREC: Challenging targets in rare earth metal-organic chemistry

Equipment

Australian Synchrotron

Cite this