Synthesis and structural characterisation of lithium, zinc, and aluminium pyrazolate complexes

Nazli E. Rad; Peter C. Junk; Glen B. Deacon; Ilya V. Taidakov; Jun Wang

doi:10.1071/CH19417

Synthesis and structural characterisation of lithium, zinc, and aluminium pyrazolate complexes

Nazli E. Rad, Peter C. Junk, Glen B. Deacon, Ilya V. Taidakov, Jun Wang

School of Chemistry

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

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Abstract

The reaction of nBuLi with 3,5-dimethylpyrazole (Me₂pzH) in Et₂O or tmeda/hexane (tmeda = N,N,N′,N′-tetramethylethane-1,2-diamine) and with 3,5-dimethyl-4-nitropyrazolate (Me₂pzHNO₂) in THF results in the formation of three structurally diverse lithium pyrazolates: Namely an Et₂O-solvated tetrameric complex [Li₄(Me₂pz)₄(OEt₂)₄], bridged entirely with μ-η²:η¹-pyrazolate bonding, a hexanuclear complex [Li₆(Me₂pz)₆(tmeda)₂] with four different coordination modes (μ-η¹:η¹, μ-η²:η¹, μ₃-η¹:η²:η¹ and μ₃-η²:η²:η¹), and a new polymeric compound [Li₂(Me₂pzNO₂)₂(thf)₂]_n, with [Li₂(Me₂pzNO₂)₂(thf)₂] groups linked by-NO₂ coordination. A mononuclear zinc complex [Zn(tBu₂pz)₂(tBu₂pzH)₂].1/2THF (tBu₂pzH = 3,5-di-tert-butylpyrazole) was prepared by reaction of tBu₂pzH with ZnEt₂, unidentate tBu₂pz groups being stabilised by N-H⋯N hydrogen bonding. Treatment of 3,5-diphenylpyrazole (Ph₂pzH) with trimethylaluminium (mole ratio 3: 1) in THF led to the formation of dinuclear [AlMe₂(μ-Ph₂pz)]₂.1/2THF.

Original language	English
Pages (from-to)	520-528
Number of pages	9
Journal	Australian Journal of Chemistry
Volume	73
Issue number	6
DOIs	https://doi.org/10.1071/CH19417
Publication status	Published - 14 Jan 2020

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10.1071/CH19417

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@article{c0ea6f3094f24b4099aebcc87b42db31,

title = "Synthesis and structural characterisation of lithium, zinc, and aluminium pyrazolate complexes",

abstract = "The reaction of nBuLi with 3,5-dimethylpyrazole (Me2pzH) in Et2O or tmeda/hexane (tmeda = N,N,N′,N′-tetramethylethane-1,2-diamine) and with 3,5-dimethyl-4-nitropyrazolate (Me2pzHNO2) in THF results in the formation of three structurally diverse lithium pyrazolates: Namely an Et2O-solvated tetrameric complex [Li4(Me2pz)4(OEt2)4], bridged entirely with μ-η2:η1-pyrazolate bonding, a hexanuclear complex [Li6(Me2pz)6(tmeda)2] with four different coordination modes (μ-η1:η1, μ-η2:η1, μ3-η1:η2:η1 and μ3-η2:η2:η1), and a new polymeric compound [Li2(Me2pzNO2)2(thf)2]n, with [Li2(Me2pzNO2)2(thf)2] groups linked by-NO2 coordination. A mononuclear zinc complex [Zn(tBu2pz)2(tBu2pzH)2].1/2THF (tBu2pzH = 3,5-di-tert-butylpyrazole) was prepared by reaction of tBu2pzH with ZnEt2, unidentate tBu2pz groups being stabilised by N-H⋯N hydrogen bonding. Treatment of 3,5-diphenylpyrazole (Ph2pzH) with trimethylaluminium (mole ratio 3: 1) in THF led to the formation of dinuclear [AlMe2(μ-Ph2pz)]2.1/2THF.",

author = "Rad, {Nazli E.} and Junk, {Peter C.} and Deacon, {Glen B.} and Taidakov, {Ilya V.} and Jun Wang",

year = "2020",

month = jan,

day = "14",

doi = "10.1071/CH19417",

language = "English",

volume = "73",

pages = "520--528",

journal = "Australian Journal of Chemistry",

issn = "0004-9425",

publisher = "CSIRO Publishing",

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TY - JOUR

T1 - Synthesis and structural characterisation of lithium, zinc, and aluminium pyrazolate complexes

AU - Rad, Nazli E.

AU - Junk, Peter C.

AU - Deacon, Glen B.

AU - Taidakov, Ilya V.

AU - Wang, Jun

PY - 2020/1/14

Y1 - 2020/1/14

N2 - The reaction of nBuLi with 3,5-dimethylpyrazole (Me2pzH) in Et2O or tmeda/hexane (tmeda = N,N,N′,N′-tetramethylethane-1,2-diamine) and with 3,5-dimethyl-4-nitropyrazolate (Me2pzHNO2) in THF results in the formation of three structurally diverse lithium pyrazolates: Namely an Et2O-solvated tetrameric complex [Li4(Me2pz)4(OEt2)4], bridged entirely with μ-η2:η1-pyrazolate bonding, a hexanuclear complex [Li6(Me2pz)6(tmeda)2] with four different coordination modes (μ-η1:η1, μ-η2:η1, μ3-η1:η2:η1 and μ3-η2:η2:η1), and a new polymeric compound [Li2(Me2pzNO2)2(thf)2]n, with [Li2(Me2pzNO2)2(thf)2] groups linked by-NO2 coordination. A mononuclear zinc complex [Zn(tBu2pz)2(tBu2pzH)2].1/2THF (tBu2pzH = 3,5-di-tert-butylpyrazole) was prepared by reaction of tBu2pzH with ZnEt2, unidentate tBu2pz groups being stabilised by N-H⋯N hydrogen bonding. Treatment of 3,5-diphenylpyrazole (Ph2pzH) with trimethylaluminium (mole ratio 3: 1) in THF led to the formation of dinuclear [AlMe2(μ-Ph2pz)]2.1/2THF.

AB - The reaction of nBuLi with 3,5-dimethylpyrazole (Me2pzH) in Et2O or tmeda/hexane (tmeda = N,N,N′,N′-tetramethylethane-1,2-diamine) and with 3,5-dimethyl-4-nitropyrazolate (Me2pzHNO2) in THF results in the formation of three structurally diverse lithium pyrazolates: Namely an Et2O-solvated tetrameric complex [Li4(Me2pz)4(OEt2)4], bridged entirely with μ-η2:η1-pyrazolate bonding, a hexanuclear complex [Li6(Me2pz)6(tmeda)2] with four different coordination modes (μ-η1:η1, μ-η2:η1, μ3-η1:η2:η1 and μ3-η2:η2:η1), and a new polymeric compound [Li2(Me2pzNO2)2(thf)2]n, with [Li2(Me2pzNO2)2(thf)2] groups linked by-NO2 coordination. A mononuclear zinc complex [Zn(tBu2pz)2(tBu2pzH)2].1/2THF (tBu2pzH = 3,5-di-tert-butylpyrazole) was prepared by reaction of tBu2pzH with ZnEt2, unidentate tBu2pz groups being stabilised by N-H⋯N hydrogen bonding. Treatment of 3,5-diphenylpyrazole (Ph2pzH) with trimethylaluminium (mole ratio 3: 1) in THF led to the formation of dinuclear [AlMe2(μ-Ph2pz)]2.1/2THF.

UR - http://www.scopus.com/inward/record.url?scp=85077984647&partnerID=8YFLogxK

U2 - 10.1071/CH19417

DO - 10.1071/CH19417

M3 - Article

AN - SCOPUS:85077984647

VL - 73

SP - 520

EP - 528

JO - Australian Journal of Chemistry

JF - Australian Journal of Chemistry

SN - 0004-9425

IS - 6

ER -

Synthesis and structural characterisation of lithium, zinc, and aluminium pyrazolate complexes

Abstract

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CTREC: Challenging targets in rare earth metal-organic chemistry

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

Australian Synchrotron

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Synthesis and structural characterisation of lithium, zinc, and aluminium pyrazolate complexes

Abstract

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Projects

CTREC: Challenging targets in rare earth metal-organic chemistry

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

Equipment

Australian Synchrotron

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