Synthesis and structural characterization of tris(phenolate)amine complexes of antimony derived from [κ4 -N (CH2 ArBu2t O)3] Sb

Bryte V. Kelly; Edward C. Weintrob; Daniela Buccella; Joseph M. Tanski; Gerard Parkin

doi:10.1016/j.inoche.2007.02.027

Synthesis and structural characterization of tris(phenolate)amine complexes of antimony derived from [κ⁴ -N (CH₂ Ar^Bu2t O)₃] Sb

Bryte V. Kelly, Edward C. Weintrob, Daniela Buccella, Joseph M. Tanski, Gerard Parkin

Chemistry

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

Abstract

The antimony aryloxide compound [κ⁴ -N (CH₂ Ar^Bu2t O)₃] Sb may be readily obtained via the reaction of Sb(OEt)₃ with tris(3,5-di-t-butyl-2-hydroxybenzyl)amine, N (CH₂ Ar^Bu2t OH)₃.[κ⁴ -N (CH₂ Ar^Bu2t O)₃] Sb forms the adduct [κ⁴ -N (CH₂ Ar^Bu2t O)₃] Sb (OSMe₂) upon treatment with Me₂SO, and comparison of the molecular structure of [κ⁴ -N (CH₂ Ar^Bu2t O)₃] Sb (OSMe₂) with that of [κ⁴-N(o-C₆H₄O)₃]Sb(OSMe₂) demonstrates that the Sb-OSMe₂ bond length in the former complex is significantly longer than that in the latter. This observation indicates that the [κ⁴ -N (CH₂ Ar^Bu2t O)₃] ligand engenders a less Lewis acidic antimony center than does [κ⁴ -N (o s(-) C₆ H₄ O)₃]. [κ⁴ -N (CH₂ Ar^Bu2t O)₃] Sb exhibits diverse reactivity. For example, treatment of [κ⁴ -N (CH₂ Ar^Bu2t O)₃] Sb with AcOH cleaves one of the Sb-O bonds to give [κ³ -N (CH₂ Ar^Bu2t O)₂ (CH₂ Ar^Bu2t OH)] Sb (κ¹ - O₂ CMe), Br₂ undergoes oxidative addition to give N (CH₂ Ar^Bu2t O)₃] SbBr₂, while Me₃NO · 2H₂O yields the oxo and hydroxo complexes {[κ⁴ -N (CH₂ Ar^Bu2t O)₃] Sb (μ -O)}₂, [κ⁴ -N (CH₂ Ar^Bu2t O)₃] Sb (OH)₂, and {[κ⁴ -N (CH₂ Ar^Bu2t O)₃] Sb^V O}₄ {Sb₄^III O₆}.

Original language	English (US)
Pages (from-to)	699-704
Number of pages	6
Journal	Inorganic Chemistry Communications
Volume	10
Issue number	6
DOIs	https://doi.org/10.1016/j.inoche.2007.02.027
State	Published - Jun 2007

Keywords

Antimony
Aryloxide
Bromide
Hydroxide
Oxo

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.inoche.2007.02.027

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@article{962a0e43ab1b437ababaf864e00e8417,

title = "Synthesis and structural characterization of tris(phenolate)amine complexes of antimony derived from [κ4 -N (CH2 ArBu2t O)3] Sb",

abstract = "The antimony aryloxide compound [κ4 -N (CH2 ArBu2t O)3] Sb may be readily obtained via the reaction of Sb(OEt)3 with tris(3,5-di-t-butyl-2-hydroxybenzyl)amine, N (CH2 ArBu2t OH)3.[κ4 -N (CH2 ArBu2t O)3] Sb forms the adduct [κ4 -N (CH2 ArBu2t O)3] Sb (OSMe2) upon treatment with Me2SO, and comparison of the molecular structure of [κ4 -N (CH2 ArBu2t O)3] Sb (OSMe2) with that of [κ4-N(o-C6H4O)3]Sb(OSMe2) demonstrates that the Sb-OSMe2 bond length in the former complex is significantly longer than that in the latter. This observation indicates that the [κ4 -N (CH2 ArBu2t O)3] ligand engenders a less Lewis acidic antimony center than does [κ4 -N (o s(-) C6 H4 O)3]. [κ4 -N (CH2 ArBu2t O)3] Sb exhibits diverse reactivity. For example, treatment of [κ4 -N (CH2 ArBu2t O)3] Sb with AcOH cleaves one of the Sb-O bonds to give [κ3 -N (CH2 ArBu2t O)2 (CH2 ArBu2t OH)] Sb (κ1 - O2 CMe), Br2 undergoes oxidative addition to give N (CH2 ArBu2t O)3] SbBr2, while Me3NO · 2H2O yields the oxo and hydroxo complexes {[κ4 -N (CH2 ArBu2t O)3] Sb (μ -O)}2, [κ4 -N (CH2 ArBu2t O)3] Sb (OH)2, and {[κ4 -N (CH2 ArBu2t O)3] SbV O}4 {Sb4III O6}.",

keywords = "Antimony, Aryloxide, Bromide, Hydroxide, Oxo",

author = "Kelly, {Bryte V.} and Weintrob, {Edward C.} and Daniela Buccella and Tanski, {Joseph M.} and Gerard Parkin",

note = "Funding Information: We thank the National Science Foundation (CHE-03-50498 and 05-21237) for support of this research. Dr. Joshua Figueroa is thanked for helpful suggestions. Copyright: Copyright 2007 Elsevier B.V., All rights reserved.",

year = "2007",

month = jun,

doi = "10.1016/j.inoche.2007.02.027",

language = "English (US)",

volume = "10",

pages = "699--704",

journal = "Inorganic Chemistry Communications",

issn = "1387-7003",

publisher = "Elsevier B.V.",

number = "6",

}

TY - JOUR

T1 - Synthesis and structural characterization of tris(phenolate)amine complexes of antimony derived from [κ4 -N (CH2 ArBu2t O)3] Sb

AU - Kelly, Bryte V.

AU - Weintrob, Edward C.

AU - Buccella, Daniela

AU - Tanski, Joseph M.

AU - Parkin, Gerard

N1 - Funding Information: We thank the National Science Foundation (CHE-03-50498 and 05-21237) for support of this research. Dr. Joshua Figueroa is thanked for helpful suggestions. Copyright: Copyright 2007 Elsevier B.V., All rights reserved.

PY - 2007/6

Y1 - 2007/6

N2 - The antimony aryloxide compound [κ4 -N (CH2 ArBu2t O)3] Sb may be readily obtained via the reaction of Sb(OEt)3 with tris(3,5-di-t-butyl-2-hydroxybenzyl)amine, N (CH2 ArBu2t OH)3.[κ4 -N (CH2 ArBu2t O)3] Sb forms the adduct [κ4 -N (CH2 ArBu2t O)3] Sb (OSMe2) upon treatment with Me2SO, and comparison of the molecular structure of [κ4 -N (CH2 ArBu2t O)3] Sb (OSMe2) with that of [κ4-N(o-C6H4O)3]Sb(OSMe2) demonstrates that the Sb-OSMe2 bond length in the former complex is significantly longer than that in the latter. This observation indicates that the [κ4 -N (CH2 ArBu2t O)3] ligand engenders a less Lewis acidic antimony center than does [κ4 -N (o s(-) C6 H4 O)3]. [κ4 -N (CH2 ArBu2t O)3] Sb exhibits diverse reactivity. For example, treatment of [κ4 -N (CH2 ArBu2t O)3] Sb with AcOH cleaves one of the Sb-O bonds to give [κ3 -N (CH2 ArBu2t O)2 (CH2 ArBu2t OH)] Sb (κ1 - O2 CMe), Br2 undergoes oxidative addition to give N (CH2 ArBu2t O)3] SbBr2, while Me3NO · 2H2O yields the oxo and hydroxo complexes {[κ4 -N (CH2 ArBu2t O)3] Sb (μ -O)}2, [κ4 -N (CH2 ArBu2t O)3] Sb (OH)2, and {[κ4 -N (CH2 ArBu2t O)3] SbV O}4 {Sb4III O6}.

AB - The antimony aryloxide compound [κ4 -N (CH2 ArBu2t O)3] Sb may be readily obtained via the reaction of Sb(OEt)3 with tris(3,5-di-t-butyl-2-hydroxybenzyl)amine, N (CH2 ArBu2t OH)3.[κ4 -N (CH2 ArBu2t O)3] Sb forms the adduct [κ4 -N (CH2 ArBu2t O)3] Sb (OSMe2) upon treatment with Me2SO, and comparison of the molecular structure of [κ4 -N (CH2 ArBu2t O)3] Sb (OSMe2) with that of [κ4-N(o-C6H4O)3]Sb(OSMe2) demonstrates that the Sb-OSMe2 bond length in the former complex is significantly longer than that in the latter. This observation indicates that the [κ4 -N (CH2 ArBu2t O)3] ligand engenders a less Lewis acidic antimony center than does [κ4 -N (o s(-) C6 H4 O)3]. [κ4 -N (CH2 ArBu2t O)3] Sb exhibits diverse reactivity. For example, treatment of [κ4 -N (CH2 ArBu2t O)3] Sb with AcOH cleaves one of the Sb-O bonds to give [κ3 -N (CH2 ArBu2t O)2 (CH2 ArBu2t OH)] Sb (κ1 - O2 CMe), Br2 undergoes oxidative addition to give N (CH2 ArBu2t O)3] SbBr2, while Me3NO · 2H2O yields the oxo and hydroxo complexes {[κ4 -N (CH2 ArBu2t O)3] Sb (μ -O)}2, [κ4 -N (CH2 ArBu2t O)3] Sb (OH)2, and {[κ4 -N (CH2 ArBu2t O)3] SbV O}4 {Sb4III O6}.

KW - Antimony

KW - Aryloxide

KW - Bromide

KW - Hydroxide

KW - Oxo

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U2 - 10.1016/j.inoche.2007.02.027

DO - 10.1016/j.inoche.2007.02.027

M3 - Article

AN - SCOPUS:34248203171

SN - 1387-7003

VL - 10

SP - 699

EP - 704

JO - Inorganic Chemistry Communications

JF - Inorganic Chemistry Communications

IS - 6

ER -