The quest for organo-alkali metal monomers: unscrambling the structure–reactivity relationship

Abstract

This perspective explores the strategies that have been employed to isolate low aggregate and, in particular, monomeric complexes of the most common alkali metal alkyls and the relationship between aggregation, structure and reactivity.

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

“…Other compositionally related alkyl compounds of the alkali metals also have different structures. , As noted by Mulvey, the observation that such compositionally related compounds may have different structures is not to be unexpected in view of the large variation in the sizes of the alkali metals, , which again underscores the significance of being able to obtain a series of carbatrane compounds, [Tism Pr i Benz ]­M, for all of the alkali metals.…”

“…In this regard, a common feature of organometallic compounds of alkali metals is their tendency to form aggregates. Monomeric derivatives are not usually encountered, and the quest for such species has recently been highlighted . Therefore, it is significant that we report here the first complete series of structurally related monomeric organometallic alkali metal compounds.…”

Super-Reducing Behavior of Benzo[b]phenothiazine Anion Under Visible-Light Photoredox Condition

“…The presence of countercation potassium in the anionic salt of BPTZ supposedly facilitates such agglomeration, which bears very close resemblance to organometallic anions under fairly concentrated solution. 32 As a proof of the aggregating behavior of BPTZ − we observe broadening of 1 H NMR peaks at a higher concentration regime (Figure S7a). Once excited at 390 nm, the absorption maximum of the pure monomer, the anion emits at 430 nm along with another broad and featureless band at 590 nm, which is attributable as its excimer (Figure 1b).…”

Carbon–Nitrogen Bond Formation Using Sodium Hexamethyldisilazide: Solvent-Dependent Reactivities and Mechanisms

“…After decades of communal disinterest in organosodium chemistry, we began trying to shine a light on its potential by expanding the toolbox for generating and using organosodium species. − This involved some minor adjustments to protocols for generating and handling sodium diisopropylamide (NaDA) , as well as developing a new reagent, sodium isopropyl­(trimethyl)­silyl amide (NaPTA), that manifests desirable solubilities and reactivities as a strong base . Our primary approach, however, is decidedly structural and mechanistic with the faith that understanding how solvation and aggregation influence reactivity and selectivity will propel applications through a combination of serendipity in our laboratory and need-driven progress by others.…”