Bromobenzene Transforms Lanthanoid Pseudo-Grignard Chemistry

Md Abdul Halim; Zhifang Guo; Glen B. Deacon; Peter C. Junk

doi:10.1002/chem.202300956

Bromobenzene Transforms Lanthanoid Pseudo-Grignard Chemistry

Md Abdul Halim
, Zhifang Guo
, Glen B. Deacon
, Peter C. Junk

School of Chemistry

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

2 Citations (Scopus)

Abstract

Divalent lanthanoid pseudo-Grignard reagents PhLnBr (Ln=Sm, Eu and Yb) can be easily prepared by the oxidative addition of bromobenzene (PhBr) to lanthanoid metals in tetrahydrofuran (THF). PhLnBr reacts with bulky N,N′-bis(2,6-di-isopropylphenyl)formamidine (DippFormH) to generate Ln^II complexes, namely [Ln(DippForm)Br(thf)₃]₂⋅6thf (1; Sm, 2; Eu), and [Yb(DippForm)Br(thf)₂]₂⋅2thf (3; Yb). Samarium and europium (in 1 and 2) are seven coordinate, whereas ytterbium (in 3) is six coordinate, and all are bromine-bridged dimers. When PhLnBr reacts with 3,5-diphenylpyrazole (Ph₂pzH), both divalent (5; [Eu(Ph₂pz)₂(thf)₄]) and trivalent (4 a; [Sm(Ph₂pz)₃(thf)₃]⋅3thf, 4 b; [Sm(Ph₂pz)₃(dme)₂]⋅dme) complexes are obtained. In the monomeric compounds 4(a,b), samarium is nine coordinate but europium is eight coordinate in 5. The use of PhLnBr in this work transforms the outcomes from earlier reactions of PhLnI.

Original language	English
Article number	e202300956
Number of pages	7
Journal	Chemistry - A European Journal
Volume	29
Issue number	36
DOIs	https://doi.org/10.1002/chem.202300956
Publication status	Published - 27 Jun 2023

Keywords

bromine-bridge dimers
crystal structures
europium
lanthanoid(II) complexes
oxidative addition
Pseudo-Grignard reagents
samarium
ytterbium

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10.1002/chem.202300956Licence: CC BY

Cite this

@article{83d36d50ec9f4d5c8c1ed560fd0d359f,

title = "Bromobenzene Transforms Lanthanoid Pseudo-Grignard Chemistry",

abstract = "Divalent lanthanoid pseudo-Grignard reagents PhLnBr (Ln=Sm, Eu and Yb) can be easily prepared by the oxidative addition of bromobenzene (PhBr) to lanthanoid metals in tetrahydrofuran (THF). PhLnBr reacts with bulky N,N′-bis(2,6-di-isopropylphenyl)formamidine (DippFormH) to generate LnII complexes, namely [Ln(DippForm)Br(thf)3]2⋅6thf (1; Sm, 2; Eu), and [Yb(DippForm)Br(thf)2]2⋅2thf (3; Yb). Samarium and europium (in 1 and 2) are seven coordinate, whereas ytterbium (in 3) is six coordinate, and all are bromine-bridged dimers. When PhLnBr reacts with 3,5-diphenylpyrazole (Ph2pzH), both divalent (5; [Eu(Ph2pz)2(thf)4]) and trivalent (4 a; [Sm(Ph2pz)3(thf)3]⋅3thf, 4 b; [Sm(Ph2pz)3(dme)2]⋅dme) complexes are obtained. In the monomeric compounds 4(a,b), samarium is nine coordinate but europium is eight coordinate in 5. The use of PhLnBr in this work transforms the outcomes from earlier reactions of PhLnI.",

keywords = "bromine-bridge dimers, crystal structures, europium, lanthanoid(II) complexes, oxidative addition, Pseudo-Grignard reagents, samarium, ytterbium",

author = "Halim, \{Md Abdul\} and Zhifang Guo and Deacon, \{Glen B.\} and Junk, \{Peter C.\}",

note = "Funding Information: PCJ and GBD gratefully acknowledge the ARC for funding (DP230100112). Parts of this research were undertaken on the MX1 beamline at the Australian Synchrotron, part of ANSTO.[33] We thank Dr Safaa Ali for preliminary studies. Open Access publishing facilitated by James Cook University, as part of the Wiley - James Cook University agreement via the Council of Australian University Librarians. Funding Information: PCJ and GBD gratefully acknowledge the ARC for funding (DP230100112). Parts of this research were undertaken on the MX1 beamline at the Australian Synchrotron, part of ANSTO. We thank Dr Safaa Ali for preliminary studies. Open Access publishing facilitated by James Cook University, as part of the Wiley ‐ James Cook University agreement via the Council of Australian University Librarians. [33] Publisher Copyright: {\textcopyright} 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.",

year = "2023",

month = jun,

day = "27",

doi = "10.1002/chem.202300956",

language = "English",

volume = "29",

journal = "Chemistry - A European Journal",

issn = "1521-3765",

publisher = "Wiley-VCH Verlag GmbH \& Co. KGaA",

number = "36",

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TY - JOUR

T1 - Bromobenzene Transforms Lanthanoid Pseudo-Grignard Chemistry

AU - Halim, Md Abdul

AU - Guo, Zhifang

AU - Deacon, Glen B.

AU - Junk, Peter C.

N1 - Funding Information: PCJ and GBD gratefully acknowledge the ARC for funding (DP230100112). Parts of this research were undertaken on the MX1 beamline at the Australian Synchrotron, part of ANSTO.[33] We thank Dr Safaa Ali for preliminary studies. Open Access publishing facilitated by James Cook University, as part of the Wiley - James Cook University agreement via the Council of Australian University Librarians. Funding Information: PCJ and GBD gratefully acknowledge the ARC for funding (DP230100112). Parts of this research were undertaken on the MX1 beamline at the Australian Synchrotron, part of ANSTO. We thank Dr Safaa Ali for preliminary studies. Open Access publishing facilitated by James Cook University, as part of the Wiley ‐ James Cook University agreement via the Council of Australian University Librarians. [33] Publisher Copyright: © 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

PY - 2023/6/27

Y1 - 2023/6/27

N2 - Divalent lanthanoid pseudo-Grignard reagents PhLnBr (Ln=Sm, Eu and Yb) can be easily prepared by the oxidative addition of bromobenzene (PhBr) to lanthanoid metals in tetrahydrofuran (THF). PhLnBr reacts with bulky N,N′-bis(2,6-di-isopropylphenyl)formamidine (DippFormH) to generate LnII complexes, namely [Ln(DippForm)Br(thf)3]2⋅6thf (1; Sm, 2; Eu), and [Yb(DippForm)Br(thf)2]2⋅2thf (3; Yb). Samarium and europium (in 1 and 2) are seven coordinate, whereas ytterbium (in 3) is six coordinate, and all are bromine-bridged dimers. When PhLnBr reacts with 3,5-diphenylpyrazole (Ph2pzH), both divalent (5; [Eu(Ph2pz)2(thf)4]) and trivalent (4 a; [Sm(Ph2pz)3(thf)3]⋅3thf, 4 b; [Sm(Ph2pz)3(dme)2]⋅dme) complexes are obtained. In the monomeric compounds 4(a,b), samarium is nine coordinate but europium is eight coordinate in 5. The use of PhLnBr in this work transforms the outcomes from earlier reactions of PhLnI.

AB - Divalent lanthanoid pseudo-Grignard reagents PhLnBr (Ln=Sm, Eu and Yb) can be easily prepared by the oxidative addition of bromobenzene (PhBr) to lanthanoid metals in tetrahydrofuran (THF). PhLnBr reacts with bulky N,N′-bis(2,6-di-isopropylphenyl)formamidine (DippFormH) to generate LnII complexes, namely [Ln(DippForm)Br(thf)3]2⋅6thf (1; Sm, 2; Eu), and [Yb(DippForm)Br(thf)2]2⋅2thf (3; Yb). Samarium and europium (in 1 and 2) are seven coordinate, whereas ytterbium (in 3) is six coordinate, and all are bromine-bridged dimers. When PhLnBr reacts with 3,5-diphenylpyrazole (Ph2pzH), both divalent (5; [Eu(Ph2pz)2(thf)4]) and trivalent (4 a; [Sm(Ph2pz)3(thf)3]⋅3thf, 4 b; [Sm(Ph2pz)3(dme)2]⋅dme) complexes are obtained. In the monomeric compounds 4(a,b), samarium is nine coordinate but europium is eight coordinate in 5. The use of PhLnBr in this work transforms the outcomes from earlier reactions of PhLnI.

KW - bromine-bridge dimers

KW - crystal structures

KW - europium

KW - lanthanoid(II) complexes

KW - oxidative addition

KW - Pseudo-Grignard reagents

KW - samarium

KW - ytterbium

UR - https://www.scopus.com/pages/publications/85156170734

U2 - 10.1002/chem.202300956

DO - 10.1002/chem.202300956

M3 - Article

C2 - 37072374

AN - SCOPUS:85156170734

SN - 1521-3765

VL - 29

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 36

M1 - e202300956

ER -

Bromobenzene Transforms Lanthanoid Pseudo-Grignard Chemistry

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Advancing the chemistry of rare earths - an Australian resource

Australian Synchrotron

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Bromobenzene Transforms Lanthanoid Pseudo-Grignard Chemistry

Abstract

Keywords

Access to Document

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Advancing the chemistry of rare earths - an Australian resource

Equipment

Australian Synchrotron

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