Functionalised Alkaline Earth Iodides from Grignard Synthons “PhAeI(thf)                         n                         ” (Ae = Mg-Ba)

Caspar N. de Bruin-Dickason; Glen B. Deacon; Cameron Jones; Peter C. Junk; Michal Wiecko

doi:10.1002/ejic.201801489

Functionalised Alkaline Earth Iodides from Grignard Synthons “PhAeI(thf) _n ” (Ae = Mg-Ba)

Caspar N. de Bruin-Dickason, Glen B. Deacon, Cameron Jones, Peter C. Junk, Michal Wiecko

School of Chemistry

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

7 Citations (Scopus)

Abstract

Derivatisation of Grignard synthons “PhAeI(thf) _n ” (Ae = Mg-Ba) prepared in situ from reactions of metal filings and iodobenzene provides a one-pot synthesis of heteroleptic N donor alkaline earth iodide complexes. Protolysis of “PhAeI(thf) _n ” with 3,5-diphenylpyrazole (Ph ₂ pzH) yields pyrazolate complexes [Mg ₂ (µ-Ph ₂ pz) ₂ (I) ₂ (thf) ₃ ] (1), [Ae(Ph ₂ pz)(I)(thf) ₄ ] (Ae = Ca (2), Sr (3)), and [Ba ₂ (Ph ₂ pz) ₂ (µ-I) ₂ (thf) ₈ ] (4). Addition of the Ae-Ph moiety to carbodiimide MesN=C=NMes (Mes = 2,4,6-(CH ₃ ) ₃ C ₆ H ₂ ) gave a series of benzamidinate iodide complexes [Ca ₂ {(MesN) ₂ CPh} ₂ (µ-I) ₂ (thf) ₄ ] (6), [Sr{(MesN) ₂ CPh}(I)(thf) ₄ ] (7), and [{Ba{(MesN) ₂ CPh}(µ-I)(thf) ₃ } _∞ ] (8). By contrast a symmetrical magnesium complex [Mg{(MesN) ₂ CPh} ₂ (thf)] (5) was obtained by Schlenk redistribution. These syntheses proceed without pre-activation of the metal for strontium and barium, and after activation with 2 mol-% iodine for calcium. The heavy alkaline earth metal complexes are the first examples of heteroleptic halide pyrazolate or amidinate complexes for strontium and barium. Complexes 1, 3, 4 and 6–8 were characterised crystallographically, revealing diverse structural chemistry of heteroleptic amidinate and pyrazolate iodide complexes across the alkaline earth series. A highlight is [Ba{(MesN) ₂ CPh}(µ-I)(thf) ₃ ] _∞ (8) – an iodide bridged infinite 1-D polymer.

Original language	English
Pages (from-to)	1030-1038
Number of pages	9
Journal	European Journal of Inorganic Chemistry
Volume	2019
Issue number	7
DOIs	https://doi.org/10.1002/ejic.201801489
Publication status	Published - 21 Feb 2019

Keywords

Alkaline earth metals
Heavy Grignard chemistry
N ligands
Structure elucidation

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10.1002/ejic.201801489

Cite this

@article{ac304103bc264136abe1893f5dbd10e1,

title = "Functionalised Alkaline Earth Iodides from Grignard Synthons “PhAeI(thf) n ” (Ae = Mg-Ba)",

abstract = " Derivatisation of Grignard synthons “PhAeI(thf) n ” (Ae = Mg-Ba) prepared in situ from reactions of metal filings and iodobenzene provides a one-pot synthesis of heteroleptic N donor alkaline earth iodide complexes. Protolysis of “PhAeI(thf) n ” with 3,5-diphenylpyrazole (Ph 2 pzH) yields pyrazolate complexes [Mg 2 (µ-Ph 2 pz) 2 (I) 2 (thf) 3 ] (1), [Ae(Ph 2 pz)(I)(thf) 4 ] (Ae = Ca (2), Sr (3)), and [Ba 2 (Ph 2 pz) 2 (µ-I) 2 (thf) 8 ] (4). Addition of the Ae-Ph moiety to carbodiimide MesN=C=NMes (Mes = 2,4,6-(CH 3 ) 3 C 6 H 2 ) gave a series of benzamidinate iodide complexes [Ca 2 {(MesN) 2 CPh} 2 (µ-I) 2 (thf) 4 ] (6), [Sr{(MesN) 2 CPh}(I)(thf) 4 ] (7), and [{Ba{(MesN) 2 CPh}(µ-I)(thf) 3 } ∞ ] (8). By contrast a symmetrical magnesium complex [Mg{(MesN) 2 CPh} 2 (thf)] (5) was obtained by Schlenk redistribution. These syntheses proceed without pre-activation of the metal for strontium and barium, and after activation with 2 mol-% iodine for calcium. The heavy alkaline earth metal complexes are the first examples of heteroleptic halide pyrazolate or amidinate complexes for strontium and barium. Complexes 1, 3, 4 and 6–8 were characterised crystallographically, revealing diverse structural chemistry of heteroleptic amidinate and pyrazolate iodide complexes across the alkaline earth series. A highlight is [Ba{(MesN) 2 CPh}(µ-I)(thf) 3 ] ∞ (8) – an iodide bridged infinite 1-D polymer. ",

keywords = "Alkaline earth metals, Heavy Grignard chemistry, N ligands, Structure elucidation",

author = "{de Bruin-Dickason}, {Caspar N.} and Deacon, {Glen B.} and Cameron Jones and Junk, {Peter C.} and Michal Wiecko",

year = "2019",

month = feb,

day = "21",

doi = "10.1002/ejic.201801489",

language = "English",

volume = "2019",

pages = "1030--1038",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

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

number = "7",

}

Functionalised Alkaline Earth Iodides from Grignard Synthons “PhAeI(thf) _n ” (Ae = Mg-Ba). / de Bruin-Dickason, Caspar N.; Deacon, Glen B.; Jones, Cameron et al.
In: European Journal of Inorganic Chemistry, Vol. 2019, No. 7, 21.02.2019, p. 1030-1038.

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

TY - JOUR

T1 - Functionalised Alkaline Earth Iodides from Grignard Synthons “PhAeI(thf) n ” (Ae = Mg-Ba)

AU - de Bruin-Dickason, Caspar N.

AU - Deacon, Glen B.

AU - Jones, Cameron

AU - Junk, Peter C.

AU - Wiecko, Michal

PY - 2019/2/21

Y1 - 2019/2/21

N2 - Derivatisation of Grignard synthons “PhAeI(thf) n ” (Ae = Mg-Ba) prepared in situ from reactions of metal filings and iodobenzene provides a one-pot synthesis of heteroleptic N donor alkaline earth iodide complexes. Protolysis of “PhAeI(thf) n ” with 3,5-diphenylpyrazole (Ph 2 pzH) yields pyrazolate complexes [Mg 2 (µ-Ph 2 pz) 2 (I) 2 (thf) 3 ] (1), [Ae(Ph 2 pz)(I)(thf) 4 ] (Ae = Ca (2), Sr (3)), and [Ba 2 (Ph 2 pz) 2 (µ-I) 2 (thf) 8 ] (4). Addition of the Ae-Ph moiety to carbodiimide MesN=C=NMes (Mes = 2,4,6-(CH 3 ) 3 C 6 H 2 ) gave a series of benzamidinate iodide complexes [Ca 2 {(MesN) 2 CPh} 2 (µ-I) 2 (thf) 4 ] (6), [Sr{(MesN) 2 CPh}(I)(thf) 4 ] (7), and [{Ba{(MesN) 2 CPh}(µ-I)(thf) 3 } ∞ ] (8). By contrast a symmetrical magnesium complex [Mg{(MesN) 2 CPh} 2 (thf)] (5) was obtained by Schlenk redistribution. These syntheses proceed without pre-activation of the metal for strontium and barium, and after activation with 2 mol-% iodine for calcium. The heavy alkaline earth metal complexes are the first examples of heteroleptic halide pyrazolate or amidinate complexes for strontium and barium. Complexes 1, 3, 4 and 6–8 were characterised crystallographically, revealing diverse structural chemistry of heteroleptic amidinate and pyrazolate iodide complexes across the alkaline earth series. A highlight is [Ba{(MesN) 2 CPh}(µ-I)(thf) 3 ] ∞ (8) – an iodide bridged infinite 1-D polymer.

AB - Derivatisation of Grignard synthons “PhAeI(thf) n ” (Ae = Mg-Ba) prepared in situ from reactions of metal filings and iodobenzene provides a one-pot synthesis of heteroleptic N donor alkaline earth iodide complexes. Protolysis of “PhAeI(thf) n ” with 3,5-diphenylpyrazole (Ph 2 pzH) yields pyrazolate complexes [Mg 2 (µ-Ph 2 pz) 2 (I) 2 (thf) 3 ] (1), [Ae(Ph 2 pz)(I)(thf) 4 ] (Ae = Ca (2), Sr (3)), and [Ba 2 (Ph 2 pz) 2 (µ-I) 2 (thf) 8 ] (4). Addition of the Ae-Ph moiety to carbodiimide MesN=C=NMes (Mes = 2,4,6-(CH 3 ) 3 C 6 H 2 ) gave a series of benzamidinate iodide complexes [Ca 2 {(MesN) 2 CPh} 2 (µ-I) 2 (thf) 4 ] (6), [Sr{(MesN) 2 CPh}(I)(thf) 4 ] (7), and [{Ba{(MesN) 2 CPh}(µ-I)(thf) 3 } ∞ ] (8). By contrast a symmetrical magnesium complex [Mg{(MesN) 2 CPh} 2 (thf)] (5) was obtained by Schlenk redistribution. These syntheses proceed without pre-activation of the metal for strontium and barium, and after activation with 2 mol-% iodine for calcium. The heavy alkaline earth metal complexes are the first examples of heteroleptic halide pyrazolate or amidinate complexes for strontium and barium. Complexes 1, 3, 4 and 6–8 were characterised crystallographically, revealing diverse structural chemistry of heteroleptic amidinate and pyrazolate iodide complexes across the alkaline earth series. A highlight is [Ba{(MesN) 2 CPh}(µ-I)(thf) 3 ] ∞ (8) – an iodide bridged infinite 1-D polymer.

KW - Alkaline earth metals

KW - Heavy Grignard chemistry

KW - N ligands

KW - Structure elucidation

UR - http://www.scopus.com/inward/record.url?scp=85060196830&partnerID=8YFLogxK

U2 - 10.1002/ejic.201801489

DO - 10.1002/ejic.201801489

M3 - Article

AN - SCOPUS:85060196830

SN - 1434-1948

VL - 2019

SP - 1030

EP - 1038

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 7

ER -

Functionalised Alkaline Earth Iodides from Grignard Synthons “PhAeI(thf) _n ” (Ae = Mg-Ba)

Abstract

Keywords

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Reactive metal-organics embracing the rare earth and alkaline earth metals

Australian Synchrotron

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Functionalised Alkaline Earth Iodides from Grignard Synthons “PhAeI(thf) n ” (Ae = Mg-Ba)

Abstract

Keywords

Access to Document

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Reactive metal-organics embracing the rare earth and alkaline earth metals

Equipment

Australian Synchrotron

Cite this

Functionalised Alkaline Earth Iodides from Grignard Synthons “PhAeI(thf) _n ” (Ae = Mg-Ba)