Direct Reaction – One Step Route to Synthesize Lanthanoid-iodide Formamidinates**

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

doi:10.1002/asia.202300333

Direct Reaction – One Step Route to Synthesize Lanthanoid-iodide Formamidinates**

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

School of Chemistry

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

1 Citation (Scopus)

Abstract

This paper describes a novel and simple method – direct reaction of lanthanoid metals with equimolar amounts of iodine and a formamidine under ultrasonication as an effective, metal-based route to lanthanoid(III) diiodide formamidinates, namely I. N,N′-Bis(2,6-diisopropylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(DippForm)I₂(thf)₃] (Ln=La, 1, Ce, 2, Tb, 3, Ho, 4, Er, 5, Tm, 6); II. N,N′-Bis(2,6-diethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(EtForm)I₂(thf)₃] (Ln=Ce, 7, Nd, 8, Gd, 9, Tb, 10, Dy, 11, Ho, 12, Er, 13, Lu, 14). III. N,N′-bis(2,6-dimethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(XylForm)I₂(thf)₃] (Ln=Ce, 15, Nd, 16, Gd, 17, Tm, 18, Lu 19); IV. N,N′-bis(phenyl)formamidinatodiiodidolanthanoid complexes [Ln(PhForm)I₂(thf)₃] (Ln=Nd, 20, Gd, 21, Er, 22). Compound [Ce(XylForm)₂I(thf)₂] (23) was also synthesized by the same method except the ratio of I₂ to XylFormH was 1 : 4. Divalent N,N′-bis(2,6-diisopropylphenyl)formamidinato-iodido-lanthanoid(II) complexes [Eu(DippForm)I(thf)₄] ⋅ thf (24), [Yb(DippForm)I(thf)₃] ⋅ 2DippFormH (25), [Sm(DippForm)I(thf)₄] ⋅ thf (26) have also been synthesized by direct reactions of the free metals, iodine and DippFormH. Interestingly, [Sm(DippForm)I₂(thf)₃] (27) was obtained by the oxidation of [Sm(DippForm)I(thf)₄] ⋅ thf (26) on exposure to air. N,N′-Bis(2,6-dimethylphenyl)formamidinatoiodidosamarium(II) [Sm(XylForm)I(thf)₃]_n (28) was also prepared by direct reaction of Sm, iodine and XylFormH (mole ratio of I₂: XylFormH=1 : 2). All products have been identified by X-ray crystallography and all the trivalent complexes [Ln(Form)_nI_3-n] (n=1 or 2) are stable to rearrangement.

Original language	English
Article number	e202300333
Number of pages	10
Journal	Chemistry - An Asian Journal
Volume	18
Issue number	14
DOIs	https://doi.org/10.1002/asia.202300333
Publication status	Published - 17 Jul 2023

Keywords

heteroleptic compounds
Lanthanoids
Rare earths
structures
synthesis

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10.1002/asia.202300333Licence: CC BY-NC-ND

Cite this

@article{03f0e62fd63c4c8c9afd7d13e7cf3852,

title = "Direct Reaction – One Step Route to Synthesize Lanthanoid-iodide Formamidinates**",

abstract = "This paper describes a novel and simple method – direct reaction of lanthanoid metals with equimolar amounts of iodine and a formamidine under ultrasonication as an effective, metal-based route to lanthanoid(III) diiodide formamidinates, namely I. N,N′-Bis(2,6-diisopropylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(DippForm)I2(thf)3] (Ln=La, 1, Ce, 2, Tb, 3, Ho, 4, Er, 5, Tm, 6); II. N,N′-Bis(2,6-diethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(EtForm)I2(thf)3] (Ln=Ce, 7, Nd, 8, Gd, 9, Tb, 10, Dy, 11, Ho, 12, Er, 13, Lu, 14). III. N,N′-bis(2,6-dimethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(XylForm)I2(thf)3] (Ln=Ce, 15, Nd, 16, Gd, 17, Tm, 18, Lu 19); IV. N,N′-bis(phenyl)formamidinatodiiodidolanthanoid complexes [Ln(PhForm)I2(thf)3] (Ln=Nd, 20, Gd, 21, Er, 22). Compound [Ce(XylForm)2I(thf)2] (23) was also synthesized by the same method except the ratio of I2 to XylFormH was 1 : 4. Divalent N,N′-bis(2,6-diisopropylphenyl)formamidinato-iodido-lanthanoid(II) complexes [Eu(DippForm)I(thf)4] ⋅ thf (24), [Yb(DippForm)I(thf)3] ⋅ 2DippFormH (25), [Sm(DippForm)I(thf)4] ⋅ thf (26) have also been synthesized by direct reactions of the free metals, iodine and DippFormH. Interestingly, [Sm(DippForm)I2(thf)3] (27) was obtained by the oxidation of [Sm(DippForm)I(thf)4] ⋅ thf (26) on exposure to air. N,N′-Bis(2,6-dimethylphenyl)formamidinatoiodidosamarium(II) [Sm(XylForm)I(thf)3]n (28) was also prepared by direct reaction of Sm, iodine and XylFormH (mole ratio of I2: XylFormH=1 : 2). All products have been identified by X-ray crystallography and all the trivalent complexes [Ln(Form)nI3-n] (n=1 or 2) are stable to rearrangement.",

keywords = "heteroleptic compounds, Lanthanoids, Rare earths, structures, synthesis",

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

note = "Funding Information: PCJ, GBD and VLB gratefully acknowledge the ARC for funding (DP230100112). Parts of this research were undertaken on the MX1 beamline at the Australian Synchrotron, part of ANSTO.[26] 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, GBD and VLB gratefully acknowledge the ARC for funding (DP230100112). Parts of this research were undertaken on the MX1 beamline at the Australian Synchrotron, part of ANSTO. Open Access publishing facilitated by James Cook University, as part of the Wiley ‐ James Cook University agreement via the Council of Australian University Librarians. [26] Publisher Copyright: {\textcopyright} 2023 The Authors. Chemistry - An Asian Journal published by Wiley-VCH GmbH.",

year = "2023",

month = jul,

day = "17",

doi = "10.1002/asia.202300333",

language = "English",

volume = "18",

journal = "Chemistry - An Asian Journal",

issn = "1861-4728",

publisher = "Wiley-Blackwell",

number = "14",

}

TY - JOUR

T1 - Direct Reaction – One Step Route to Synthesize Lanthanoid-iodide Formamidinates**

AU - Guo, Zhifang

AU - Halim, Md Abdul

AU - Blair, Victoria L.

AU - Deacon, Glen B.

AU - Junk, Peter C.

N1 - Funding Information: PCJ, GBD and VLB gratefully acknowledge the ARC for funding (DP230100112). Parts of this research were undertaken on the MX1 beamline at the Australian Synchrotron, part of ANSTO.[26] 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, GBD and VLB gratefully acknowledge the ARC for funding (DP230100112). Parts of this research were undertaken on the MX1 beamline at the Australian Synchrotron, part of ANSTO. Open Access publishing facilitated by James Cook University, as part of the Wiley ‐ James Cook University agreement via the Council of Australian University Librarians. [26] Publisher Copyright: © 2023 The Authors. Chemistry - An Asian Journal published by Wiley-VCH GmbH.

PY - 2023/7/17

Y1 - 2023/7/17

N2 - This paper describes a novel and simple method – direct reaction of lanthanoid metals with equimolar amounts of iodine and a formamidine under ultrasonication as an effective, metal-based route to lanthanoid(III) diiodide formamidinates, namely I. N,N′-Bis(2,6-diisopropylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(DippForm)I2(thf)3] (Ln=La, 1, Ce, 2, Tb, 3, Ho, 4, Er, 5, Tm, 6); II. N,N′-Bis(2,6-diethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(EtForm)I2(thf)3] (Ln=Ce, 7, Nd, 8, Gd, 9, Tb, 10, Dy, 11, Ho, 12, Er, 13, Lu, 14). III. N,N′-bis(2,6-dimethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(XylForm)I2(thf)3] (Ln=Ce, 15, Nd, 16, Gd, 17, Tm, 18, Lu 19); IV. N,N′-bis(phenyl)formamidinatodiiodidolanthanoid complexes [Ln(PhForm)I2(thf)3] (Ln=Nd, 20, Gd, 21, Er, 22). Compound [Ce(XylForm)2I(thf)2] (23) was also synthesized by the same method except the ratio of I2 to XylFormH was 1 : 4. Divalent N,N′-bis(2,6-diisopropylphenyl)formamidinato-iodido-lanthanoid(II) complexes [Eu(DippForm)I(thf)4] ⋅ thf (24), [Yb(DippForm)I(thf)3] ⋅ 2DippFormH (25), [Sm(DippForm)I(thf)4] ⋅ thf (26) have also been synthesized by direct reactions of the free metals, iodine and DippFormH. Interestingly, [Sm(DippForm)I2(thf)3] (27) was obtained by the oxidation of [Sm(DippForm)I(thf)4] ⋅ thf (26) on exposure to air. N,N′-Bis(2,6-dimethylphenyl)formamidinatoiodidosamarium(II) [Sm(XylForm)I(thf)3]n (28) was also prepared by direct reaction of Sm, iodine and XylFormH (mole ratio of I2: XylFormH=1 : 2). All products have been identified by X-ray crystallography and all the trivalent complexes [Ln(Form)nI3-n] (n=1 or 2) are stable to rearrangement.

AB - This paper describes a novel and simple method – direct reaction of lanthanoid metals with equimolar amounts of iodine and a formamidine under ultrasonication as an effective, metal-based route to lanthanoid(III) diiodide formamidinates, namely I. N,N′-Bis(2,6-diisopropylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(DippForm)I2(thf)3] (Ln=La, 1, Ce, 2, Tb, 3, Ho, 4, Er, 5, Tm, 6); II. N,N′-Bis(2,6-diethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(EtForm)I2(thf)3] (Ln=Ce, 7, Nd, 8, Gd, 9, Tb, 10, Dy, 11, Ho, 12, Er, 13, Lu, 14). III. N,N′-bis(2,6-dimethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(XylForm)I2(thf)3] (Ln=Ce, 15, Nd, 16, Gd, 17, Tm, 18, Lu 19); IV. N,N′-bis(phenyl)formamidinatodiiodidolanthanoid complexes [Ln(PhForm)I2(thf)3] (Ln=Nd, 20, Gd, 21, Er, 22). Compound [Ce(XylForm)2I(thf)2] (23) was also synthesized by the same method except the ratio of I2 to XylFormH was 1 : 4. Divalent N,N′-bis(2,6-diisopropylphenyl)formamidinato-iodido-lanthanoid(II) complexes [Eu(DippForm)I(thf)4] ⋅ thf (24), [Yb(DippForm)I(thf)3] ⋅ 2DippFormH (25), [Sm(DippForm)I(thf)4] ⋅ thf (26) have also been synthesized by direct reactions of the free metals, iodine and DippFormH. Interestingly, [Sm(DippForm)I2(thf)3] (27) was obtained by the oxidation of [Sm(DippForm)I(thf)4] ⋅ thf (26) on exposure to air. N,N′-Bis(2,6-dimethylphenyl)formamidinatoiodidosamarium(II) [Sm(XylForm)I(thf)3]n (28) was also prepared by direct reaction of Sm, iodine and XylFormH (mole ratio of I2: XylFormH=1 : 2). All products have been identified by X-ray crystallography and all the trivalent complexes [Ln(Form)nI3-n] (n=1 or 2) are stable to rearrangement.

KW - heteroleptic compounds

KW - Lanthanoids

KW - Rare earths

KW - structures

KW - synthesis

UR - https://www.scopus.com/pages/publications/85160262302

U2 - 10.1002/asia.202300333

DO - 10.1002/asia.202300333

M3 - Article

C2 - 37203372

AN - SCOPUS:85160262302

SN - 1861-4728

VL - 18

JO - Chemistry - An Asian Journal

JF - Chemistry - An Asian Journal

IS - 14

M1 - e202300333

ER -

Direct Reaction – One Step Route to Synthesize Lanthanoid-iodide Formamidinates**

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Advancing the chemistry of rare earths - an Australian resource

Australian Synchrotron

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Direct Reaction – One Step Route to Synthesize Lanthanoid-iodide Formamidinates**

Abstract

Keywords

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Advancing the chemistry of rare earths - an Australian resource

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Australian Synchrotron

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