Alkali Metals: Inorganic Chemistry

Abstract

This article is updated to cover the literature in the area of inorganic chemistry of alkali metals since 2006. The advancement in instrumentation and spectroscopic techniques in recent two decades has provided researchers with more powerful tools for structure determination of compounds. In this respect, mixed‐sandwich electrides of alkali metals, complexes with dimers or chains of alkali metal anions, electrides with alkali metal ions intercalated into zeolites, and interstitial hydride enclosed by an unusual (Li + ) 8 cubic cage and a simpler more defined LiH ‐containing complex have recently been reported in the literature. Alkali metal ozonides, mixed alkali metal ozonide superoxide, and alkali metal suboxides have also been reported. The preparation of Na 3 N , K 3 N , ternary and higher nitride compounds of lithium are included in this article. The exact composition of “ NaB 6 ” and “ KB 6 ” is also included. The role of alkali metals in trielide clusters of traditional Zintl polyanions has been shown. Synthesis and structures of trimetallic Li–Na–K amide‐alkoxide compounds, alkoxide compounds, enolates, and highly aggregated cage structures of lithium‐heavier alkali metal alkoxides and heterotrimetallic alkoxide are included.

Mechanochemical Nucleophilic Substitution of Alcohols via Isouronium Intermediates

“…Higher nucleophilic reactivity of F − in CsF compared to KF also correlates with lower lattice energy for the former (CsF, 740 kJ•mol −1 ; KF, 821 kJ mol −1 ). 62 Use of potassium phenolate as the nucleophile resulted in a modest 46% yield of the corresponding substitution product 45 (Eq. 4).…”

Hydrogen production via reaction of metals with supercritical water

“…By contrast, the hydroxides that form in reaction of water with alkali and alkaline metals are soluble in water. 21,22 As the metals of the alkali group increase in atomic mass, the hydroxides they form increase in solubility in water which means that the formed hydroxides have no passivation effect. 22 Instead, metal is continuously exposed to the oxidizer until the metal is completely consumed.…”

“…21,22 As the metals of the alkali group increase in atomic mass, the hydroxides they form increase in solubility in water which means that the formed hydroxides have no passivation effect. 22 Instead, metal is continuously exposed to the oxidizer until the metal is completely consumed. This is also the case with aluminum hydroxides: as temperature increases, aluminum hydroxides also decline in cohesiveness and ability to passivate, thereby allowing for increased reaction efficiency.…”

Theoretical Study on the Electronic Structure of Heavy Alkali-Metal Suboxides

“…20 These compounds are generated as a result of the partial oxidation of the pure alkali metal or the reaction with their normal oxide phase. 21 They exist as a thermodynamically stable phase, yet they are reactive, as exemplified by their high sensitivity to air, moisture, and temperature. 8 At temperatures lower than 150 K, the amorphous phases of Rb and Cs suboxides are known to form and they are regarded as a metallic-glass state.…”

“…For Cs, four stable suboxide phases have been synthesized: Cs 3 O, Cs 11 O 3 , Cs 4 O, and Cs 7 O . These compounds are generated as a result of the partial oxidation of the pure alkali metal or the reaction with their normal oxide phase . They exist as a thermodynamically stable phase, yet they are reactive, as exemplified by their high sensitivity to air, moisture, and temperature …”