Applications of the method of continuous variations—MCV or the Method of Job—to problems of interest to organometallic chemists are described. MCV provides qualitative and quantitative insights into the stoichiometries underlying association of m molecules of A and n molecules of B to form AmBn. Applications to complex ensembles probe associations that form metal clusters and aggregates. Job plots in which reaction rates are monitored provide relative stoichiometries in rate-limiting transition structures. In a specialized variant, ligand- or solvent-dependent reaction rates are dissected into contributions in both the ground states and transition states, which affords insights into the full reaction coordinate from a single Job plot. Gaps in the literature are identified and critiqued.

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The method of continuous variation (MCV) in conjunction with 6Li NMR spectroscopy was used to characterize four lithium phenolates solvated by a range of solvents including N,N,N′,N′-tetramethylethylenediamine, Et2O, pyridine, protic amines, alcohols, and highly dipolar aprotic solvents. Dimers, trimers, and tetramers were observed, depending on the precise lithium phenolate-solvent combinations. Competition experiments (solvent swaps) provide insights into relative solvation energies propensities toward mixed solvation.

The method of continuous variation in conjunction with 1H and 19F NMR spectroscopies was used to characterize lithium and sodium enolates solvated by N,N,N′,N′-tetramethylethyldiamine (TMEDA) and tetrahydrofuran (THF). A strategy developed using lithium enolates was then applied to the more challenging sodium enolates. A number of sodium enolates solvated by TMEDA or THF afford exclusively tetramers. Evidence suggests that TMEDA chelates sodium on cubic tetramers.

Dieser Aufsatz beschreibt Anwendungen der Methode der kontinuierlichen Variation (MCV oder Job‐Plots) auf Fragen der metallorganischen Chemie. Die MCV bietet qualitative und quantitative Einblicke in die Stöchiometrien, die der Assoziation von m Molekülen A und n Molekülen B zur Bildung von AmBn zugrunde liegen. Auch komplexere Fälle von Metallclustern und Aggregaten sind beschreibbar. Job‐Plots, in denen Reaktionsgeschwindigkeiten verfolgt werden, liefern relative Stöchiometrien geschwindigkeitsbestimmender Übergangsstrukturen. In einer speziellen Variante werden von den Liganden oder dem Lösungsmittel abhängige Reaktionsgeschwindigkeiten in Grundzustands‐ und Übergangszustandsbeiträge aufgegliedert, was einen Einblick in die vollständige Reaktionskoordinate mithilfe eines einzigen Job‐Plots ermöglicht. Die Lücken in der Literatur werden aufgezeigt und besprochen.