Synthesis and Structure of Heavy Alkali Metal Pentalenides

Hugh J. Sanderson; Sumanta Banerjee; Mandeep Kaur; Alan R. Kennedy; Gabriele Kociok-Köhn; Ulrich Hintermair; Stuart D. Robertson

doi:10.1002/zaac.202400039

Synthesis and Structure of Heavy Alkali Metal Pentalenides

Hugh J. Sanderson, Sumanta Banerjee, Mandeep Kaur, Alan R. Kennedy, Gabriele Kociok-Köhn, Ulrich Hintermair, Stuart D. Robertson

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

Abstract

The solid-state structures of the first rubidium and caesium pentalenides [Rb(THF)]₂[Ph₄Pn] and [Cs(THF)]₂[Ph₄Pn] have been determined by single crystal X-ray diffraction. Both were found to be polymeric in the solid state through interactions of the cations with the phenyl substituents, in contrast to their lighter group 1 congeners which are monomeric for lithium and sodium, and THF-bridged for potassium. Both [Rb(THF)]₂[Ph₄Pn] and [Cs(THF)]₂[Ph₄Pn] displayed increased η⁸ coordination, demonstrating a shift towards higher hapticities down the group as previously predicted computationally for the parent M₂[Pn] complexes (M=group 1 metal). The solid-state structures of the polydentate donor adducts [M(DME)_x]₂[Ph₄Pn] (M=Li, x=1; M=Na, x=2) and [M(Me₆TREN)]₂[Ph₄Pn] (M=K, Rb, Cs) were all monomeric and displayed increased metal-carbon distances and decreased ring slippage values relative to the THF adducts.

Original language	English
Article number	e202400039
Number of pages	8
Journal	Zeitschrift fur Anorganische und Allgemeine Chemie
Early online date	14 Aug 2024
DOIs	https://doi.org/10.1002/zaac.202400039
Publication status	E-pub ahead of print - 14 Aug 2024

Data Availability Statement

The data that support the findings of this study are available in the supplementary material of this article.

Keywords

Alkali Metal Coordination
Caesium
Pentalenides
Rubidium

ASJC Scopus subject areas

Inorganic Chemistry

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title = "Synthesis and Structure of Heavy Alkali Metal Pentalenides",

abstract = "The solid-state structures of the first rubidium and caesium pentalenides [Rb(THF)]2[Ph4Pn] and [Cs(THF)]2[Ph4Pn] have been determined by single crystal X-ray diffraction. Both were found to be polymeric in the solid state through interactions of the cations with the phenyl substituents, in contrast to their lighter group 1 congeners which are monomeric for lithium and sodium, and THF-bridged for potassium. Both [Rb(THF)]2[Ph4Pn] and [Cs(THF)]2[Ph4Pn] displayed increased η8 coordination, demonstrating a shift towards higher hapticities down the group as previously predicted computationally for the parent M2[Pn] complexes (M=group 1 metal). The solid-state structures of the polydentate donor adducts [M(DME)x]2[Ph4Pn] (M=Li, x=1; M=Na, x=2) and [M(Me6TREN)]2[Ph4Pn] (M=K, Rb, Cs) were all monomeric and displayed increased metal-carbon distances and decreased ring slippage values relative to the THF adducts.",

keywords = "Alkali Metal Coordination, Caesium, Pentalenides, Rubidium",

author = "Sanderson, {Hugh J.} and Sumanta Banerjee and Mandeep Kaur and Kennedy, {Alan R.} and Gabriele Kociok-K{\"o}hn and Ulrich Hintermair and Robertson, {Stuart D.}",

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T1 - Synthesis and Structure of Heavy Alkali Metal Pentalenides

AU - Sanderson, Hugh J.

AU - Banerjee, Sumanta

AU - Kaur, Mandeep

AU - Kennedy, Alan R.

AU - Kociok-Köhn, Gabriele

AU - Hintermair, Ulrich

AU - Robertson, Stuart D.

PY - 2024/8/14

Y1 - 2024/8/14

N2 - The solid-state structures of the first rubidium and caesium pentalenides [Rb(THF)]2[Ph4Pn] and [Cs(THF)]2[Ph4Pn] have been determined by single crystal X-ray diffraction. Both were found to be polymeric in the solid state through interactions of the cations with the phenyl substituents, in contrast to their lighter group 1 congeners which are monomeric for lithium and sodium, and THF-bridged for potassium. Both [Rb(THF)]2[Ph4Pn] and [Cs(THF)]2[Ph4Pn] displayed increased η8 coordination, demonstrating a shift towards higher hapticities down the group as previously predicted computationally for the parent M2[Pn] complexes (M=group 1 metal). The solid-state structures of the polydentate donor adducts [M(DME)x]2[Ph4Pn] (M=Li, x=1; M=Na, x=2) and [M(Me6TREN)]2[Ph4Pn] (M=K, Rb, Cs) were all monomeric and displayed increased metal-carbon distances and decreased ring slippage values relative to the THF adducts.

AB - The solid-state structures of the first rubidium and caesium pentalenides [Rb(THF)]2[Ph4Pn] and [Cs(THF)]2[Ph4Pn] have been determined by single crystal X-ray diffraction. Both were found to be polymeric in the solid state through interactions of the cations with the phenyl substituents, in contrast to their lighter group 1 congeners which are monomeric for lithium and sodium, and THF-bridged for potassium. Both [Rb(THF)]2[Ph4Pn] and [Cs(THF)]2[Ph4Pn] displayed increased η8 coordination, demonstrating a shift towards higher hapticities down the group as previously predicted computationally for the parent M2[Pn] complexes (M=group 1 metal). The solid-state structures of the polydentate donor adducts [M(DME)x]2[Ph4Pn] (M=Li, x=1; M=Na, x=2) and [M(Me6TREN)]2[Ph4Pn] (M=K, Rb, Cs) were all monomeric and displayed increased metal-carbon distances and decreased ring slippage values relative to the THF adducts.

KW - Alkali Metal Coordination

KW - Caesium

KW - Pentalenides

KW - Rubidium

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M3 - Article

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ER -

Synthesis and Structure of Heavy Alkali Metal Pentalenides

Abstract

Data Availability Statement

Keywords

ASJC Scopus subject areas

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