Can Bismuth Replace Mercury in Redox Transmetallation/Protolysis Syntheses from Free Lanthanoid Metals?

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Abstract

Tris(pentafluorophenyl)bismuth has been examined as a potential replacement for diarylmercurials in redox transmetallation/protolysis (RTP) syntheses of reactive rare earth compounds from free rare earth metals, HgAr2, and a proligand HL. Thus, the lanthanoid pyrazolates, [Ln(Ph2pz)3(thf)3] (Ph2pz=3,5-diphenylpyrazolate; Ln=La, 1, Ce, 2, Nd, 3, Tb, 4; thf=tetrahydrofuran), [Ln2(Ph2pz)4(OMe)2(dme)2]⋅2 dme (Ln=Ho, 5, Er, 6, Tm, 7, Lu, 8; dme=1,2-dimethoxyethane), [Ln(Ph2pz)3(dme)2] (Ln=Dy, 9, Sm, 10), [Ln(tBu2pz)3(thf)2] (tBu2pz=3,5-di-tert-butylpyrazolate; Ln=La, 11, Ce, 12, Sm, 13, Gd, 14, Dy, 15, Ho, 16, Tm, 17, Yb, 18, Lu, 19), [Ln(ttfpz)3(thf)3] (ttfpz=3-(2′-thienyl)-5-(trifluoromethyl)pyrazolate; Ln=La, 20, Sm, 21), and [Er(PhMepz)3(thf)2] 22 (PhMepz=3-phenyl-5-methylpyrazolate) have been prepared in good yields by redox transmetallation/protolysis reactions employing lanthanoid metals and trispentafluorophenylbismuth [Bi(C6F5)3]⋅0.5 diox (diox=1, 4-dioxane) in donor solvents. This is a new and efficient synthetic route in which Bi(C6F5)3 replaces the commonly used Hg(C6F5)2 or HgPh2, and provides proof of concept for the method. [Ln2(Ph2pz)4(OMe)2(dme)2]⋅2 dme (5–8) complexes are derived from C−O bond activation of dme on crystallization of the initial products from this solvent, and are dimeric methoxide-bridged species. Other structures are monomeric with η2-bound pyrazolate ligands and nine-coordinate metal atoms for complexes 1–4, 9–10 and 20–21, and eight-coordinate metal atoms for complexes 11–19 and 22.

Original languageEnglish
Pages (from-to)17464-17474
Number of pages11
JournalChemistry - A European Journal
Volume24
Issue number66
DOIs
Publication statusPublished - 27 Nov 2018

Keywords

  • crystal structures
  • lanthanoid metals
  • lanthanoid pyrazolates.
  • new synthetic method
  • redox transmetallation/protolysis (RTP) reactions
  • trispentafluorophenylbismuth (Bi(CF))

Cite this

@article{d47dcee62561433a92b8a47801e91dbb,
title = "Can Bismuth Replace Mercury in Redox Transmetallation/Protolysis Syntheses from Free Lanthanoid Metals?",
abstract = "Tris(pentafluorophenyl)bismuth has been examined as a potential replacement for diarylmercurials in redox transmetallation/protolysis (RTP) syntheses of reactive rare earth compounds from free rare earth metals, HgAr2, and a proligand HL. Thus, the lanthanoid pyrazolates, [Ln(Ph2pz)3(thf)3] (Ph2pz=3,5-diphenylpyrazolate; Ln=La, 1, Ce, 2, Nd, 3, Tb, 4; thf=tetrahydrofuran), [Ln2(Ph2pz)4(OMe)2(dme)2]⋅2 dme (Ln=Ho, 5, Er, 6, Tm, 7, Lu, 8; dme=1,2-dimethoxyethane), [Ln(Ph2pz)3(dme)2] (Ln=Dy, 9, Sm, 10), [Ln(tBu2pz)3(thf)2] (tBu2pz=3,5-di-tert-butylpyrazolate; Ln=La, 11, Ce, 12, Sm, 13, Gd, 14, Dy, 15, Ho, 16, Tm, 17, Yb, 18, Lu, 19), [Ln(ttfpz)3(thf)3] (ttfpz=3-(2′-thienyl)-5-(trifluoromethyl)pyrazolate; Ln=La, 20, Sm, 21), and [Er(PhMepz)3(thf)2] 22 (PhMepz=3-phenyl-5-methylpyrazolate) have been prepared in good yields by redox transmetallation/protolysis reactions employing lanthanoid metals and trispentafluorophenylbismuth [Bi(C6F5)3]⋅0.5 diox (diox=1, 4-dioxane) in donor solvents. This is a new and efficient synthetic route in which Bi(C6F5)3 replaces the commonly used Hg(C6F5)2 or HgPh2, and provides proof of concept for the method. [Ln2(Ph2pz)4(OMe)2(dme)2]⋅2 dme (5–8) complexes are derived from C−O bond activation of dme on crystallization of the initial products from this solvent, and are dimeric methoxide-bridged species. Other structures are monomeric with η2-bound pyrazolate ligands and nine-coordinate metal atoms for complexes 1–4, 9–10 and 20–21, and eight-coordinate metal atoms for complexes 11–19 and 22.",
keywords = "crystal structures, lanthanoid metals, lanthanoid pyrazolates., new synthetic method, redox transmetallation/protolysis (RTP) reactions, trispentafluorophenylbismuth (Bi(CF))",
author = "Zhifang Guo and Victoria Blair and Deacon, {Glen B.} and Junk, {Peter C.}",
year = "2018",
month = "11",
day = "27",
doi = "10.1002/chem.201804703",
language = "English",
volume = "24",
pages = "17464--17474",
journal = "Chemistry - A European Journal",
issn = "1521-3765",
publisher = "Wiley-VCH Verlag GmbH & Co. KGaA",
number = "66",

}

Can Bismuth Replace Mercury in Redox Transmetallation/Protolysis Syntheses from Free Lanthanoid Metals? / Guo, Zhifang; Blair, Victoria; Deacon, Glen B.; Junk, Peter C.

In: Chemistry - A European Journal, Vol. 24, No. 66, 27.11.2018, p. 17464-17474.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Can Bismuth Replace Mercury in Redox Transmetallation/Protolysis Syntheses from Free Lanthanoid Metals?

AU - Guo, Zhifang

AU - Blair, Victoria

AU - Deacon, Glen B.

AU - Junk, Peter C.

PY - 2018/11/27

Y1 - 2018/11/27

N2 - Tris(pentafluorophenyl)bismuth has been examined as a potential replacement for diarylmercurials in redox transmetallation/protolysis (RTP) syntheses of reactive rare earth compounds from free rare earth metals, HgAr2, and a proligand HL. Thus, the lanthanoid pyrazolates, [Ln(Ph2pz)3(thf)3] (Ph2pz=3,5-diphenylpyrazolate; Ln=La, 1, Ce, 2, Nd, 3, Tb, 4; thf=tetrahydrofuran), [Ln2(Ph2pz)4(OMe)2(dme)2]⋅2 dme (Ln=Ho, 5, Er, 6, Tm, 7, Lu, 8; dme=1,2-dimethoxyethane), [Ln(Ph2pz)3(dme)2] (Ln=Dy, 9, Sm, 10), [Ln(tBu2pz)3(thf)2] (tBu2pz=3,5-di-tert-butylpyrazolate; Ln=La, 11, Ce, 12, Sm, 13, Gd, 14, Dy, 15, Ho, 16, Tm, 17, Yb, 18, Lu, 19), [Ln(ttfpz)3(thf)3] (ttfpz=3-(2′-thienyl)-5-(trifluoromethyl)pyrazolate; Ln=La, 20, Sm, 21), and [Er(PhMepz)3(thf)2] 22 (PhMepz=3-phenyl-5-methylpyrazolate) have been prepared in good yields by redox transmetallation/protolysis reactions employing lanthanoid metals and trispentafluorophenylbismuth [Bi(C6F5)3]⋅0.5 diox (diox=1, 4-dioxane) in donor solvents. This is a new and efficient synthetic route in which Bi(C6F5)3 replaces the commonly used Hg(C6F5)2 or HgPh2, and provides proof of concept for the method. [Ln2(Ph2pz)4(OMe)2(dme)2]⋅2 dme (5–8) complexes are derived from C−O bond activation of dme on crystallization of the initial products from this solvent, and are dimeric methoxide-bridged species. Other structures are monomeric with η2-bound pyrazolate ligands and nine-coordinate metal atoms for complexes 1–4, 9–10 and 20–21, and eight-coordinate metal atoms for complexes 11–19 and 22.

AB - Tris(pentafluorophenyl)bismuth has been examined as a potential replacement for diarylmercurials in redox transmetallation/protolysis (RTP) syntheses of reactive rare earth compounds from free rare earth metals, HgAr2, and a proligand HL. Thus, the lanthanoid pyrazolates, [Ln(Ph2pz)3(thf)3] (Ph2pz=3,5-diphenylpyrazolate; Ln=La, 1, Ce, 2, Nd, 3, Tb, 4; thf=tetrahydrofuran), [Ln2(Ph2pz)4(OMe)2(dme)2]⋅2 dme (Ln=Ho, 5, Er, 6, Tm, 7, Lu, 8; dme=1,2-dimethoxyethane), [Ln(Ph2pz)3(dme)2] (Ln=Dy, 9, Sm, 10), [Ln(tBu2pz)3(thf)2] (tBu2pz=3,5-di-tert-butylpyrazolate; Ln=La, 11, Ce, 12, Sm, 13, Gd, 14, Dy, 15, Ho, 16, Tm, 17, Yb, 18, Lu, 19), [Ln(ttfpz)3(thf)3] (ttfpz=3-(2′-thienyl)-5-(trifluoromethyl)pyrazolate; Ln=La, 20, Sm, 21), and [Er(PhMepz)3(thf)2] 22 (PhMepz=3-phenyl-5-methylpyrazolate) have been prepared in good yields by redox transmetallation/protolysis reactions employing lanthanoid metals and trispentafluorophenylbismuth [Bi(C6F5)3]⋅0.5 diox (diox=1, 4-dioxane) in donor solvents. This is a new and efficient synthetic route in which Bi(C6F5)3 replaces the commonly used Hg(C6F5)2 or HgPh2, and provides proof of concept for the method. [Ln2(Ph2pz)4(OMe)2(dme)2]⋅2 dme (5–8) complexes are derived from C−O bond activation of dme on crystallization of the initial products from this solvent, and are dimeric methoxide-bridged species. Other structures are monomeric with η2-bound pyrazolate ligands and nine-coordinate metal atoms for complexes 1–4, 9–10 and 20–21, and eight-coordinate metal atoms for complexes 11–19 and 22.

KW - crystal structures

KW - lanthanoid metals

KW - lanthanoid pyrazolates.

KW - new synthetic method

KW - redox transmetallation/protolysis (RTP) reactions

KW - trispentafluorophenylbismuth (Bi(CF))

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U2 - 10.1002/chem.201804703

DO - 10.1002/chem.201804703

M3 - Article

VL - 24

SP - 17464

EP - 17474

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 1521-3765

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ER -