A close look at short C-CH3⋯potassium contacts: Synthetic and theoretical investigations of [M2Co2(μ 3-OtBu)2(μ2-OtBu)4(thf) n] (M = Na, K, Rb, thf=tetrahydrofuran)

Christopher E. Anson; Wim Klopper; Jin Shan Li; Lukasz Ponikiewski; Alexander Rothenberger

doi:10.1002/chem.200500603

A close look at short C-CH₃⋯potassium contacts: Synthetic and theoretical investigations of [M₂Co₂(μ ₃-OtBu)₂(μ₂-OtBu)₄(thf) _n] (M = Na, K, Rb, thf=tetrahydrofuran)

Christopher E. Anson, Wim Klopper^*, Jin Shan Li, Lukasz Ponikiewski, Alexander Rothenberger

^*Corresponding author for this work

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

13 Scopus citations

Abstract

Agostic interactions of the type Si-CH₃⋯M⁺ (M=alkali metal) arc frequently mentioned in discussions of solid-state structures of trimethylsilyl compounds and the purpose of this work was to elucidate if they also exist in the related tert-butyl species by using density functional theory. The compounds [M₂Co₂(μ₃- OtBu)₂(μ₂-OtBu)₄(thf)_n] (M = Na, n = 2; M = K, n = 0; M = Rb, n = 1) have been synthesised and their crystal structures determined. Close contacts of methyl groups with K atoms are observed in the solid-state structure of [K₂Co₂(μ₃- OtBu)₂(μ₂OtBu)₄], and calculations of the rotational barrier of a tert-butoxy group about the axis through the C-O bond were performed. It was shown that apparent short C-CH₃⋯K distances are in this case a consequence of the packing in the extended solid-state structure.

Original language	English (US)
Pages (from-to)	2032-2038
Number of pages	7
Journal	Chemistry - A European Journal
Volume	12
Issue number	7
DOIs	https://doi.org/10.1002/chem.200500603
State	Published - Feb 20 2006
Externally published	Yes

Keywords

Agostic interactions
Alkali metals
Density functional calculations
Metal alkoxides

ASJC Scopus subject areas

Catalysis
Organic Chemistry

Access to Document

10.1002/chem.200500603

Cite this

@article{1e11c5824de74cef8ce3ef26fef32eee,

title = "A close look at short C-CH3⋯potassium contacts: Synthetic and theoretical investigations of [M2Co2(μ 3-OtBu)2(μ2-OtBu)4(thf) n] (M = Na, K, Rb, thf=tetrahydrofuran)",

abstract = "Agostic interactions of the type Si-CH3⋯M+ (M=alkali metal) arc frequently mentioned in discussions of solid-state structures of trimethylsilyl compounds and the purpose of this work was to elucidate if they also exist in the related tert-butyl species by using density functional theory. The compounds [M2Co2(μ3- OtBu)2(μ2-OtBu)4(thf)n] (M = Na, n = 2; M = K, n = 0; M = Rb, n = 1) have been synthesised and their crystal structures determined. Close contacts of methyl groups with K atoms are observed in the solid-state structure of [K2Co2(μ3- OtBu)2(μ2OtBu)4], and calculations of the rotational barrier of a tert-butoxy group about the axis through the C-O bond were performed. It was shown that apparent short C-CH3⋯K distances are in this case a consequence of the packing in the extended solid-state structure.",

keywords = "Agostic interactions, Alkali metals, Density functional calculations, Metal alkoxides",

author = "Anson, {Christopher E.} and Wim Klopper and Li, {Jin Shan} and Lukasz Ponikiewski and Alexander Rothenberger",

year = "2006",

month = feb,

day = "20",

doi = "10.1002/chem.200500603",

language = "English (US)",

volume = "12",

pages = "2032--2038",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "7",

}

A close look at short C-CH₃⋯potassium contacts: Synthetic and theoretical investigations of [M₂Co₂(μ ₃-OtBu)₂(μ₂-OtBu)₄(thf) _n] (M = Na, K, Rb, thf=tetrahydrofuran). / Anson, Christopher E.; Klopper, Wim; Li, Jin Shan et al.
In: Chemistry - A European Journal, Vol. 12, No. 7, 20.02.2006, p. 2032-2038.

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

TY - JOUR

T1 - A close look at short C-CH3⋯potassium contacts

T2 - Synthetic and theoretical investigations of [M2Co2(μ 3-OtBu)2(μ2-OtBu)4(thf) n] (M = Na, K, Rb, thf=tetrahydrofuran)

AU - Anson, Christopher E.

AU - Klopper, Wim

AU - Li, Jin Shan

AU - Ponikiewski, Lukasz

AU - Rothenberger, Alexander

PY - 2006/2/20

Y1 - 2006/2/20

N2 - Agostic interactions of the type Si-CH3⋯M+ (M=alkali metal) arc frequently mentioned in discussions of solid-state structures of trimethylsilyl compounds and the purpose of this work was to elucidate if they also exist in the related tert-butyl species by using density functional theory. The compounds [M2Co2(μ3- OtBu)2(μ2-OtBu)4(thf)n] (M = Na, n = 2; M = K, n = 0; M = Rb, n = 1) have been synthesised and their crystal structures determined. Close contacts of methyl groups with K atoms are observed in the solid-state structure of [K2Co2(μ3- OtBu)2(μ2OtBu)4], and calculations of the rotational barrier of a tert-butoxy group about the axis through the C-O bond were performed. It was shown that apparent short C-CH3⋯K distances are in this case a consequence of the packing in the extended solid-state structure.

AB - Agostic interactions of the type Si-CH3⋯M+ (M=alkali metal) arc frequently mentioned in discussions of solid-state structures of trimethylsilyl compounds and the purpose of this work was to elucidate if they also exist in the related tert-butyl species by using density functional theory. The compounds [M2Co2(μ3- OtBu)2(μ2-OtBu)4(thf)n] (M = Na, n = 2; M = K, n = 0; M = Rb, n = 1) have been synthesised and their crystal structures determined. Close contacts of methyl groups with K atoms are observed in the solid-state structure of [K2Co2(μ3- OtBu)2(μ2OtBu)4], and calculations of the rotational barrier of a tert-butoxy group about the axis through the C-O bond were performed. It was shown that apparent short C-CH3⋯K distances are in this case a consequence of the packing in the extended solid-state structure.

KW - Agostic interactions

KW - Alkali metals

KW - Density functional calculations

KW - Metal alkoxides

UR - http://www.scopus.com/inward/record.url?scp=33644554489&partnerID=8YFLogxK

U2 - 10.1002/chem.200500603

DO - 10.1002/chem.200500603

M3 - Article

C2 - 16370003

AN - SCOPUS:33644554489

SN - 0947-6539

VL - 12

SP - 2032

EP - 2038

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 7

ER -