Organometallic Complexes of the Alkali Metals

Alkali Metal Carbatrane Compounds [TismPriBenz]M: Synthesis and Structural Characterization of a Complete Series of Monomeric Alkali Metal Alkyl Compounds

“…Organolithium compounds are, without doubt, an important class of molecules, in large part due to their use as alkyl or aryl transfer reagents in both organic and inorganic chemistry. − By comparison, organometallic compounds of the heavier congeners have received much less attention. − For example, with respect to structurally characterized alkali metal compounds that are listed in the Cambridge Structural Database (CSD), while there are approximately 1,000 occurrences of Li–C single bonds, there are fewer than 50 occurrences of Cs–C single bonds . Despite this prominence of organolithium chemistry, however, Mulvey has drawn attention to the chemistry of the heavier congeners, by noting the useful roles that these metals have in a variety of catalytic applications; as such, it is pertinent to develop further the chemistry of the heavier alkali metals.…”

Uncovering the Untapped Potential of the Use of Sodium Amides for Regioselective Arene Functionalisation

“…With an increased focus on sustainability in organometallic chemistry and the superior reactivity expected for these reagents, the interest on the preparation and the properties of more abundant sodium (and potassium) organometallic compounds have significantly increased in recent years. [6] Several studies have proved the enormous potential of these reagents in deprotonative metalation reactions, both as a single component [7] or in combination with another divalent metal such as Zn, [8] Mg [9] or Fe. [10] Despite their enhanced reactivity, heavier alkali-metal amides still struggle to efficiently metalate less reactive substrates, such as non-activated arenes.…”

Organolithium aggregation as a blueprint to construct polynuclear lithium nickelate clusters

“…Contrastingly, there have been limited applications to date that take advantage of the high aggregation of organo-alkalimetal compounds. Numerous studies and reviews have been documented that assess the aggregation of organo-alkali-metal compounds in solution and the solid-state, [1][2][3]6 yet lithium acetylides are comparatively underexplored in this domain. [7][8][9] In 1987, Weiss and co-workers reported that t Bu-CRC-Li can form THFsolvated tetrameric and dodecameric aggregates in the solid-state simply depending on the crystallisation conditions employed.…”

“…2c), but also contains regions in which the Li cations are occupationally disordered across two or more positions. Several other aliphatic lithium acetylides were also explored; cycloalkyl (propyl, pentyl, and hexyl) lithium acetylides all gave insoluble and intractable solids however, whilst i Pr-CRC-Li (10 equivalents) afforded mixed acetylide/alkoxide cluster [Li 10 (Et 2 O) 2 Ni(CRC-i Pr) 8 (CRC-Me 2 O)] 2 (6), albeit in low yields (see the ESI † for the full structure). Attempts to prepare or crystallise the polynuclear lithium nickelate clusters from THF were unsuccessful, supporting the crucial role of aggregation in the construction of these complexes.…”