Redox transmetallation approaches to the synthesis of extremely bulky amido-lanthanoid(II) and -calcium(II) complexes

Caspar N. De Bruin-Dickason, Aaron J. Boutland, Deepak Dange, Glen B. Deacon, Cameron Jones

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Redox transmetallation protolysis reactions between HgPh2, elemental metals, M = Ca, Eu, or Yb, and the bulkyl arylsilylamine PhLH (HN(SiPh3)(Ar), Ar = C6H2Pri{C(H)Ph2}2-4,2,6), or the borylsilylamine PhLBoH (HN(SiPh3){B(DipNCH)2}, Dip = C6H3Pri 2-2,6) pro-ligands yielded complexes incorporating doubly deprotonated, N,C-chelating amido/organyl ligands, viz. [M(L-H) (thf)x]n, L-H = PhL†-H (1-3) or PhLBo-H (4-5); M = Ca (1, 4), Eu (2) or Yb (3, 5); x = 0 (5) or 2 (1-4); n = 1 (1-4) or 2 (5). Structural differences between 4 and 5 represent a rare divergence in the chemistry of divalent calcium and ytterbium. Utilisation of a less hindered bis(aryl) amine, DLMH (HN(Dip)(Mes), Mes = C6H2Me3-2,4,6) in a similar reaction yielded a three-coordinate, trigonal planar ytterbium complex [Yb(DLM)2(thf)] (6). Direct redox transmetallation reactions between an amido-mercurial iodide [(MeL)HgI] (7, MeL =-N(SiMe3)(Ar)) and ytterbium or europium metal afforded homoleptic [Yb(MeL)2] (8) and heteroleptic [{Eu(MeL)(μ-I)(thf)}2] (9) respectively. This study highlights the versatility of redox transmetallation pathways to amido-lanthanoid complexes, especially where such compounds are difficult to access using conventional salt metathesis pathways.

Original languageEnglish
Pages (from-to)9512-9520
Number of pages9
JournalDalton Transactions
Volume47
Issue number28
DOIs
Publication statusPublished - 1 Jan 2018

Cite this

@article{40f9f8610f124170a5e7a336b99051dd,
title = "Redox transmetallation approaches to the synthesis of extremely bulky amido-lanthanoid(II) and -calcium(II) complexes",
abstract = "Redox transmetallation protolysis reactions between HgPh2, elemental metals, M = Ca, Eu, or Yb, and the bulkyl arylsilylamine PhL†H (HN(SiPh3)(Ar†), Ar† = C6H2Pri{C(H)Ph2}2-4,2,6), or the borylsilylamine PhLBoH (HN(SiPh3){B(DipNCH)2}, Dip = C6H3Pri 2-2,6) pro-ligands yielded complexes incorporating doubly deprotonated, N,C-chelating amido/organyl ligands, viz. [M(L-H) (thf)x]n, L-H = PhL†-H (1-3) or PhLBo-H (4-5); M = Ca (1, 4), Eu (2) or Yb (3, 5); x = 0 (5) or 2 (1-4); n = 1 (1-4) or 2 (5). Structural differences between 4 and 5 represent a rare divergence in the chemistry of divalent calcium and ytterbium. Utilisation of a less hindered bis(aryl) amine, DLMH (HN(Dip)(Mes), Mes = C6H2Me3-2,4,6) in a similar reaction yielded a three-coordinate, trigonal planar ytterbium complex [Yb(DLM)2(thf)] (6). Direct redox transmetallation reactions between an amido-mercurial iodide [(MeL†)HgI] (7, MeL† =-N(SiMe3)(Ar†)) and ytterbium or europium metal afforded homoleptic [Yb(MeL†)2] (8) and heteroleptic [{Eu(MeL†)(μ-I)(thf)}2] (9) respectively. This study highlights the versatility of redox transmetallation pathways to amido-lanthanoid complexes, especially where such compounds are difficult to access using conventional salt metathesis pathways.",
author = "{De Bruin-Dickason}, {Caspar N.} and Boutland, {Aaron J.} and Deepak Dange and Deacon, {Glen B.} and Cameron Jones",
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doi = "10.1039/c8dt02138d",
language = "English",
volume = "47",
pages = "9512--9520",
journal = "Journal of the Chemical Society. Dalton Transactions",
issn = "1477-9226",
publisher = "The Royal Society of Chemistry",
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Redox transmetallation approaches to the synthesis of extremely bulky amido-lanthanoid(II) and -calcium(II) complexes. / De Bruin-Dickason, Caspar N.; Boutland, Aaron J.; Dange, Deepak; Deacon, Glen B.; Jones, Cameron.

In: Dalton Transactions, Vol. 47, No. 28, 01.01.2018, p. 9512-9520.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Redox transmetallation approaches to the synthesis of extremely bulky amido-lanthanoid(II) and -calcium(II) complexes

AU - De Bruin-Dickason, Caspar N.

AU - Boutland, Aaron J.

AU - Dange, Deepak

AU - Deacon, Glen B.

AU - Jones, Cameron

PY - 2018/1/1

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N2 - Redox transmetallation protolysis reactions between HgPh2, elemental metals, M = Ca, Eu, or Yb, and the bulkyl arylsilylamine PhL†H (HN(SiPh3)(Ar†), Ar† = C6H2Pri{C(H)Ph2}2-4,2,6), or the borylsilylamine PhLBoH (HN(SiPh3){B(DipNCH)2}, Dip = C6H3Pri 2-2,6) pro-ligands yielded complexes incorporating doubly deprotonated, N,C-chelating amido/organyl ligands, viz. [M(L-H) (thf)x]n, L-H = PhL†-H (1-3) or PhLBo-H (4-5); M = Ca (1, 4), Eu (2) or Yb (3, 5); x = 0 (5) or 2 (1-4); n = 1 (1-4) or 2 (5). Structural differences between 4 and 5 represent a rare divergence in the chemistry of divalent calcium and ytterbium. Utilisation of a less hindered bis(aryl) amine, DLMH (HN(Dip)(Mes), Mes = C6H2Me3-2,4,6) in a similar reaction yielded a three-coordinate, trigonal planar ytterbium complex [Yb(DLM)2(thf)] (6). Direct redox transmetallation reactions between an amido-mercurial iodide [(MeL†)HgI] (7, MeL† =-N(SiMe3)(Ar†)) and ytterbium or europium metal afforded homoleptic [Yb(MeL†)2] (8) and heteroleptic [{Eu(MeL†)(μ-I)(thf)}2] (9) respectively. This study highlights the versatility of redox transmetallation pathways to amido-lanthanoid complexes, especially where such compounds are difficult to access using conventional salt metathesis pathways.

AB - Redox transmetallation protolysis reactions between HgPh2, elemental metals, M = Ca, Eu, or Yb, and the bulkyl arylsilylamine PhL†H (HN(SiPh3)(Ar†), Ar† = C6H2Pri{C(H)Ph2}2-4,2,6), or the borylsilylamine PhLBoH (HN(SiPh3){B(DipNCH)2}, Dip = C6H3Pri 2-2,6) pro-ligands yielded complexes incorporating doubly deprotonated, N,C-chelating amido/organyl ligands, viz. [M(L-H) (thf)x]n, L-H = PhL†-H (1-3) or PhLBo-H (4-5); M = Ca (1, 4), Eu (2) or Yb (3, 5); x = 0 (5) or 2 (1-4); n = 1 (1-4) or 2 (5). Structural differences between 4 and 5 represent a rare divergence in the chemistry of divalent calcium and ytterbium. Utilisation of a less hindered bis(aryl) amine, DLMH (HN(Dip)(Mes), Mes = C6H2Me3-2,4,6) in a similar reaction yielded a three-coordinate, trigonal planar ytterbium complex [Yb(DLM)2(thf)] (6). Direct redox transmetallation reactions between an amido-mercurial iodide [(MeL†)HgI] (7, MeL† =-N(SiMe3)(Ar†)) and ytterbium or europium metal afforded homoleptic [Yb(MeL†)2] (8) and heteroleptic [{Eu(MeL†)(μ-I)(thf)}2] (9) respectively. This study highlights the versatility of redox transmetallation pathways to amido-lanthanoid complexes, especially where such compounds are difficult to access using conventional salt metathesis pathways.

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DO - 10.1039/c8dt02138d

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