Reduction of [Cp*Sb]4 with Subvalent Main-Group Metal Reductants: Syntheses and Structures of [(L1Mg)4(Sb4)] and [(L2Ga)2(Sb4)] Containing Edge-Missing Sb4 Units

Chelladurai Ganesamoorthy; Julia Krüger; Christoph Wölper; Anton S. Nizovtsev; Stephan Schulz

doi:10.1002/chem.201605547

Reduction of [Cp*Sb]₄ with Subvalent Main-Group Metal Reductants: Syntheses and Structures of [(L¹Mg)₄(Sb₄)] and [(L²Ga)₂(Sb₄)] Containing Edge-Missing Sb₄ Units

Chelladurai Ganesamoorthy, Julia Krüger, Christoph Wölper, Anton S. Nizovtsev, Stephan Schulz

Inorganic Chemistry Section

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19 Citations (Scopus)

Abstract

[Cp*Sb]₄ (Cp*=C₅Me₅) reacts with [L¹Mg]₂ and L²Ga with formation of [(L¹Mg)₄(μ₄,η^1:2:2:2-Sb₄)] (L¹=iPr₂NC[N(2,6-iPr₂C₆H₃)]₂, 1) and [(L²Ga)₂(μ,η^2:2-Sb₄)] (L²=HC[C(Me)N(2,6-iPr₂C₆H₃)]₂, 2). The cleavage of the Sb−Sb and Sb−C bonds in [Cp*Sb]₄ are the crucial steps in both reactions. The formation of 1 occurred by elimination of the Cp* anion and formation of Cp*MgL¹, while 2 was formed by reductive elimination of Cp*₂ and oxidative addition of L²Ga to the Sb₄ unit. 1 and 2 were characterized by heteronuclear NMR spectroscopy and single-crystal X-ray diffraction, and their bonding situation was studied by quantum chemical calculations.

Original language	English
Pages (from-to)	2461-2468
Number of pages	8
Journal	Chemistry - A European Journal
Volume	23
Issue number	10
DOIs	https://doi.org/10.1002/chem.201605547
Publication status	Published - 1 Jan 2017

Keywords

antimony
cluster compounds
main-group elements
subvalent compounds
Zintl ions
PHOSPHORUS
ACTIVATION
CORRELATION-ENERGY
REACTIVITY
HARTREE-FOCK
ELECTRON LOCALIZATION
ELEMENTS
CAGE COMPOUNDS
P-4
BOND

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@article{adf36c5c2838410cb1de65ba665c0fa1,

title = "Reduction of [Cp*Sb]4 with Subvalent Main-Group Metal Reductants: Syntheses and Structures of [(L1Mg)4(Sb4)] and [(L2Ga)2(Sb4)] Containing Edge-Missing Sb4 Units",

abstract = "[Cp*Sb]4 (Cp*=C5Me5) reacts with [L1Mg]2 and L2Ga with formation of [(L1Mg)4(μ4,η1:2:2:2-Sb4)] (L1=iPr2NC[N(2,6-iPr2C6H3)]2, 1) and [(L2Ga)2(μ,η2:2-Sb4)] (L2=HC[C(Me)N(2,6-iPr2C6H3)]2, 2). The cleavage of the Sb−Sb and Sb−C bonds in [Cp*Sb]4 are the crucial steps in both reactions. The formation of 1 occurred by elimination of the Cp* anion and formation of Cp*MgL1, while 2 was formed by reductive elimination of Cp*2 and oxidative addition of L2Ga to the Sb4 unit. 1 and 2 were characterized by heteronuclear NMR spectroscopy and single-crystal X-ray diffraction, and their bonding situation was studied by quantum chemical calculations.",

keywords = "antimony, cluster compounds, main-group elements, subvalent compounds, Zintl ions, PHOSPHORUS, ACTIVATION, CORRELATION-ENERGY, REACTIVITY, HARTREE-FOCK, ELECTRON LOCALIZATION, ELEMENTS, CAGE COMPOUNDS, P-4, BOND",

author = "Chelladurai Ganesamoorthy and Julia Kr{\"u}ger and Christoph W{\"o}lper and Nizovtsev, {Anton S.} and Stephan Schulz",

note = "Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2017",

month = jan,

day = "1",

doi = "10.1002/chem.201605547",

language = "English",

volume = "23",

pages = "2461--2468",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "10",

}

Reduction of [Cp*Sb]₄ with Subvalent Main-Group Metal Reductants : Syntheses and Structures of [(L¹Mg)₄(Sb₄)] and [(L²Ga)₂(Sb₄)] Containing Edge-Missing Sb₄ Units. / Ganesamoorthy, Chelladurai; Krüger, Julia; Wölper, Christoph et al.

In: Chemistry - A European Journal, Vol. 23, No. 10, 01.01.2017, p. 2461-2468.

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

TY - JOUR

T1 - Reduction of [Cp*Sb]4 with Subvalent Main-Group Metal Reductants

T2 - Syntheses and Structures of [(L1Mg)4(Sb4)] and [(L2Ga)2(Sb4)] Containing Edge-Missing Sb4 Units

AU - Ganesamoorthy, Chelladurai

AU - Krüger, Julia

AU - Wölper, Christoph

AU - Nizovtsev, Anton S.

AU - Schulz, Stephan

PY - 2017/1/1

Y1 - 2017/1/1

N2 - [Cp*Sb]4 (Cp*=C5Me5) reacts with [L1Mg]2 and L2Ga with formation of [(L1Mg)4(μ4,η1:2:2:2-Sb4)] (L1=iPr2NC[N(2,6-iPr2C6H3)]2, 1) and [(L2Ga)2(μ,η2:2-Sb4)] (L2=HC[C(Me)N(2,6-iPr2C6H3)]2, 2). The cleavage of the Sb−Sb and Sb−C bonds in [Cp*Sb]4 are the crucial steps in both reactions. The formation of 1 occurred by elimination of the Cp* anion and formation of Cp*MgL1, while 2 was formed by reductive elimination of Cp*2 and oxidative addition of L2Ga to the Sb4 unit. 1 and 2 were characterized by heteronuclear NMR spectroscopy and single-crystal X-ray diffraction, and their bonding situation was studied by quantum chemical calculations.

AB - [Cp*Sb]4 (Cp*=C5Me5) reacts with [L1Mg]2 and L2Ga with formation of [(L1Mg)4(μ4,η1:2:2:2-Sb4)] (L1=iPr2NC[N(2,6-iPr2C6H3)]2, 1) and [(L2Ga)2(μ,η2:2-Sb4)] (L2=HC[C(Me)N(2,6-iPr2C6H3)]2, 2). The cleavage of the Sb−Sb and Sb−C bonds in [Cp*Sb]4 are the crucial steps in both reactions. The formation of 1 occurred by elimination of the Cp* anion and formation of Cp*MgL1, while 2 was formed by reductive elimination of Cp*2 and oxidative addition of L2Ga to the Sb4 unit. 1 and 2 were characterized by heteronuclear NMR spectroscopy and single-crystal X-ray diffraction, and their bonding situation was studied by quantum chemical calculations.

KW - antimony

KW - cluster compounds

KW - main-group elements

KW - subvalent compounds

KW - Zintl ions

KW - PHOSPHORUS

KW - ACTIVATION

KW - CORRELATION-ENERGY

KW - REACTIVITY

KW - HARTREE-FOCK

KW - ELECTRON LOCALIZATION

KW - ELEMENTS

KW - CAGE COMPOUNDS

KW - P-4

KW - BOND

UR - http://www.scopus.com/inward/record.url?scp=85011395611&partnerID=8YFLogxK

U2 - 10.1002/chem.201605547

DO - 10.1002/chem.201605547

M3 - Article

AN - SCOPUS:85011395611

VL - 23

SP - 2461

EP - 2468

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 10

ER -

Reduction of [Cp*Sb]₄ with Subvalent Main-Group Metal Reductants: Syntheses and Structures of [(L¹Mg)₄(Sb₄)] and [(L²Ga)₂(Sb₄)] Containing Edge-Missing Sb₄ Units

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