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Banerjee, Sumanta
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article
Synthesis and Structure of Heavy Alkali Metal Pentalenides
Abstract
<p>The solid-state structures of the first rubidium and caesium pentalenides [Rb(THF)]<sub>2</sub>[Ph<sub>4</sub>Pn] and [Cs(THF)]<sub>2</sub>[Ph<sub>4</sub>Pn] 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)]<sub>2</sub>[Ph<sub>4</sub>Pn] and [Cs(THF)]<sub>2</sub>[Ph<sub>4</sub>Pn] displayed increased η<sup>8</sup> coordination, demonstrating a shift towards higher hapticities down the group as previously predicted computationally for the parent M<sub>2</sub>[Pn] complexes (M=group 1 metal). The solid-state structures of the polydentate donor adducts [M(DME)<sub>x</sub>]<sub>2</sub>[Ph<sub>4</sub>Pn] (M=Li, x=1; M=Na, x=2) and [M(Me<sub>6</sub>TREN)]<sub>2</sub>[Ph<sub>4</sub>Pn] (M=K, Rb, Cs) were all monomeric and displayed increased metal-carbon distances and decreased ring slippage values relative to the THF adducts.</p>