Enforcing Metal-Arene Interactions in Bulky p-Terphenyl Bis(anilide) Complexes of Group 2 Metals (Be-Ba): Potential Precursors for Low-Oxidation-State Alkaline Earth Metal Systems

Dat T. Nguyen; Christoph Helling; Matthew J. Evans; Cameron Jones

doi:10.1021/acs.inorgchem.4c00207

Enforcing Metal-Arene Interactions in Bulky p-Terphenyl Bis(anilide) Complexes of Group 2 Metals (Be-Ba): Potential Precursors for Low-Oxidation-State Alkaline Earth Metal Systems

Dat T. Nguyen, Christoph Helling, Matthew J. Evans, Cameron Jones

School of Chemistry

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

6 Citations (Scopus)

Abstract

An extremely bulky p-terphenyl bis(aniline), p-C₆H₄{C₆H₄[N(H)TCHP]-2}₂ (TCHP = 2,4,6-tricyclohexylphenyl) ^TCHPTerphH₂, has been developed. Deprotonation of a less bulky analogue, ^DipTerphH₂ (Dip = 2,6-diisopropylphenyl), with BePh₂ affords the bimetallic system, [(BePh)₂(μ-^DipTerph)] 1. Treating either ^TCHPTerphH₂ or ^DipTerphH₂ with Mg{CH₂(SiMe₃)}₂ gives the monomeric bis(anilide) complexes [Mg(^ArTerph)] (Ar = Dip 2, TCHP 3) which display rare examples of η⁶-arene coordination to the metal center. Treating 2 with THF leads to partial dissociation of the Mg···arene interaction and formation of [Mg(^DipTerph)(THF)] 4. Reactions of the bis(aniline)s with the group 2 metal amides [M{N(SiMe₃)₂}₂] afford dimeric, structurally analogous compounds [{M(^ArTerph)}₂] (Ar = Dip, M = Ca 5, Sr 6, Ba 7; Ar = TCHP, M = Ca 8, Sr 9, Ba 10) which display intermolecular M···arene interactions in the solid state. Computational studies have shown that the intramolecular M···η⁶-arene interactions in models of the ether-free metal bis(anilide) compounds are largely electrostatic in nature. Reductions of these compounds with alkali metals led to mixtures of unidentified products.

Original language	English
Pages (from-to)	5718–5726
Number of pages	9
Journal	Inorganic Chemistry
Volume	63
Issue number	12
DOIs	https://doi.org/10.1021/acs.inorgchem.4c00207
Publication status	Published - 12 Mar 2024

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10.1021/acs.inorgchem.4c00207

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@article{f8ab710b2db24b9ea698a3b53dc3b23b,

title = "Enforcing Metal-Arene Interactions in Bulky p-Terphenyl Bis(anilide) Complexes of Group 2 Metals (Be-Ba): Potential Precursors for Low-Oxidation-State Alkaline Earth Metal Systems",

abstract = "An extremely bulky p-terphenyl bis(aniline), p-C6H4{C6H4[N(H)TCHP]-2}2 (TCHP = 2,4,6-tricyclohexylphenyl) TCHPTerphH2, has been developed. Deprotonation of a less bulky analogue, DipTerphH2 (Dip = 2,6-diisopropylphenyl), with BePh2 affords the bimetallic system, [(BePh)2(μ-DipTerph)] 1. Treating either TCHPTerphH2 or DipTerphH2 with Mg{CH2(SiMe3)}2 gives the monomeric bis(anilide) complexes [Mg(ArTerph)] (Ar = Dip 2, TCHP 3) which display rare examples of η6-arene coordination to the metal center. Treating 2 with THF leads to partial dissociation of the Mg···arene interaction and formation of [Mg(DipTerph)(THF)] 4. Reactions of the bis(aniline)s with the group 2 metal amides [M{N(SiMe3)2}2] afford dimeric, structurally analogous compounds [{M(ArTerph)}2] (Ar = Dip, M = Ca 5, Sr 6, Ba 7; Ar = TCHP, M = Ca 8, Sr 9, Ba 10) which display intermolecular M···arene interactions in the solid state. Computational studies have shown that the intramolecular M···η6-arene interactions in models of the ether-free metal bis(anilide) compounds are largely electrostatic in nature. Reductions of these compounds with alkali metals led to mixtures of unidentified products.",

author = "Nguyen, {Dat T.} and Christoph Helling and Evans, {Matthew J.} and Cameron Jones",

note = "Publisher Copyright: {\textcopyright} 2024 American Chemical Society",

year = "2024",

month = mar,

day = "12",

doi = "10.1021/acs.inorgchem.4c00207",

language = "English",

volume = "63",

pages = "5718–5726",

journal = "Inorganic Chemistry",

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Enforcing Metal-Arene Interactions in Bulky p-Terphenyl Bis(anilide) Complexes of Group 2 Metals (Be-Ba): Potential Precursors for Low-Oxidation-State Alkaline Earth Metal Systems. / Nguyen, Dat T.; Helling, Christoph; Evans, Matthew J. et al.
In: Inorganic Chemistry, Vol. 63, No. 12, 12.03.2024, p. 5718–5726.

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

TY - JOUR

T1 - Enforcing Metal-Arene Interactions in Bulky p-Terphenyl Bis(anilide) Complexes of Group 2 Metals (Be-Ba)

T2 - Potential Precursors for Low-Oxidation-State Alkaline Earth Metal Systems

AU - Nguyen, Dat T.

AU - Helling, Christoph

AU - Evans, Matthew J.

AU - Jones, Cameron

PY - 2024/3/12

Y1 - 2024/3/12

N2 - An extremely bulky p-terphenyl bis(aniline), p-C6H4{C6H4[N(H)TCHP]-2}2 (TCHP = 2,4,6-tricyclohexylphenyl) TCHPTerphH2, has been developed. Deprotonation of a less bulky analogue, DipTerphH2 (Dip = 2,6-diisopropylphenyl), with BePh2 affords the bimetallic system, [(BePh)2(μ-DipTerph)] 1. Treating either TCHPTerphH2 or DipTerphH2 with Mg{CH2(SiMe3)}2 gives the monomeric bis(anilide) complexes [Mg(ArTerph)] (Ar = Dip 2, TCHP 3) which display rare examples of η6-arene coordination to the metal center. Treating 2 with THF leads to partial dissociation of the Mg···arene interaction and formation of [Mg(DipTerph)(THF)] 4. Reactions of the bis(aniline)s with the group 2 metal amides [M{N(SiMe3)2}2] afford dimeric, structurally analogous compounds [{M(ArTerph)}2] (Ar = Dip, M = Ca 5, Sr 6, Ba 7; Ar = TCHP, M = Ca 8, Sr 9, Ba 10) which display intermolecular M···arene interactions in the solid state. Computational studies have shown that the intramolecular M···η6-arene interactions in models of the ether-free metal bis(anilide) compounds are largely electrostatic in nature. Reductions of these compounds with alkali metals led to mixtures of unidentified products.

AB - An extremely bulky p-terphenyl bis(aniline), p-C6H4{C6H4[N(H)TCHP]-2}2 (TCHP = 2,4,6-tricyclohexylphenyl) TCHPTerphH2, has been developed. Deprotonation of a less bulky analogue, DipTerphH2 (Dip = 2,6-diisopropylphenyl), with BePh2 affords the bimetallic system, [(BePh)2(μ-DipTerph)] 1. Treating either TCHPTerphH2 or DipTerphH2 with Mg{CH2(SiMe3)}2 gives the monomeric bis(anilide) complexes [Mg(ArTerph)] (Ar = Dip 2, TCHP 3) which display rare examples of η6-arene coordination to the metal center. Treating 2 with THF leads to partial dissociation of the Mg···arene interaction and formation of [Mg(DipTerph)(THF)] 4. Reactions of the bis(aniline)s with the group 2 metal amides [M{N(SiMe3)2}2] afford dimeric, structurally analogous compounds [{M(ArTerph)}2] (Ar = Dip, M = Ca 5, Sr 6, Ba 7; Ar = TCHP, M = Ca 8, Sr 9, Ba 10) which display intermolecular M···arene interactions in the solid state. Computational studies have shown that the intramolecular M···η6-arene interactions in models of the ether-free metal bis(anilide) compounds are largely electrostatic in nature. Reductions of these compounds with alkali metals led to mixtures of unidentified products.

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DO - 10.1021/acs.inorgchem.4c00207

M3 - Article

AN - SCOPUS:85187640104

SN - 0020-1669

VL - 63

SP - 5718

EP - 5726

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 12

ER -

Enforcing Metal-Arene Interactions in Bulky p-Terphenyl Bis(anilide) Complexes of Group 2 Metals (Be-Ba): Potential Precursors for Low-Oxidation-State Alkaline Earth Metal Systems

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Enforcing Metal-Arene Interactions in Bulky p-Terphenyl Bis(anilide) Complexes of Group 2 Metals (Be-Ba): Potential Precursors for Low-Oxidation-State Alkaline Earth Metal Systems

Abstract

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