Grignard reagents RMgCl and their so-called turbo variant, the highly reactive RMgCl⋅LiCl, are of exceptional synthetic utility. Nevertheless, it is still not fully understood which species these compounds form in solution and, in particular, in which way LiCl exerts its reactivity-enhancing effect. A combination of electrospray-ionization mass spectrometry, electrical conductivity measurements, NMR spectroscopy (including diffusion-ordered spectroscopy), and quantum chemical calculations is used to analyze solutions of RMgCl (R=Me, Et, Bu, Hex, Oct, Dec, iPr, tBu, Ph) in tetrahydrofuran and other ethereal solvents in the absence and presence of stoichiometric amounts of LiCl. In tetrahydrofuran, RMgCl forms mononuclear species, which are converted into trinuclear anions as a result of the concentration increase experienced during the electrospray process. These trinuclear anions are theoretically predicted to adopt open cubic geometries, which remarkably resemble structural motifs previously found in the solid state. The molecular constituents of RMgCl and RMgCl⋅LiCl are interrelated via Schlenk equilibria and fast intermolecular exchange processes. A small portion of the Grignard reagent also forms anionic ate complexes in solution. The abundance of these more electron-rich and hence supposedly more nucleophilic ate complexes strongly increases upon the addition of LiCl, thus rationalizing its beneficial effect on the reactivity of Grignard reagents.

Palladium ate complexes are frequently invoked as important intermediates in Heck and cross-coupling reactions, but so far have largely eluded characterization at the molecular level. Here, we use electrospray-ionization mass spectrometry, electrical conductivity measurements, and NMR spectroscopy to show that the electron-poor catalyst [L Pd] (L=tris[3,5-bis(trifluoromethyl)phenyl]phosphine) readily reacts with Br ions to afford the anionic, zero-valent ate complex [L PdBr] . In contrast, more-electron-rich Pd catalysts display lower tendencies toward the formation of ate complexes. Combining [L Pd] with LiI and an aryl iodide substrate (ArI) results in the observation of the Pd ate complex [L Pd(Ar)I ] .

The reduction of Pd precatalysts to catalytically active Pd species is a key step in many palladium-mediated cross-coupling reactions. Besides phosphines, the stoichiometrically used organometallic reagents can afford this reduction, but do so in a poorly understood way. To elucidate the mechanism of this reaction, we have treated solutions of Pd(OAc) and a phosphine ligand L in tetrahydrofuran with RMgCl (R=Ph, Bn, Bu) as well as other organometallic reagents. Analysis of these model systems by electrospray- ionization mass spectrometry found palladate(II) complexes [L PdR ] (n=0 and 1), thus pointing to the occurrence of transmetallation reactions. Upon gas-phase fragmentation, the [L PdR ] anions preferentially underwent a reductive elimination to yield Pd species. The sequence of the transmetallation and reductive elimination, thus, constitutes a feasible mechanism for the reduction of the Pd(OAc) precatalyst. Other species of interest observed include the Pd complex [PdBn ] , which did not fragment via a reductive elimination but lost BnH instead.

Despite their considerable practical value, palladium/1,3‐diene‐catalyzed cross‐coupling reactions between Grignard reagents RMgCl and alkyl halides AlkylX remain mechanistically poorly understood. Herein, we probe the intermediates formed in these reactions by a combination of electrospray‐ionization mass spectrometry, UV/Vis spectroscopy, and NMR spectroscopy. According to our results and in line with previous hypotheses, the first step of the catalytic cycle brings about transmetalation to afford organopalladate anions. These organopalladate anions apparently undergo SN2‐type reactions with the AlkylX coupling partner. The resulting neutral complexes then release the cross‐coupling products by reductive elimination. In gas‐phase fragmentation experiments, the occurrence of reductive eliminations was observed for anionic analogues of the neutral complexes. Although the actual catalytic cycle is supposed to involve chiefly mononuclear palladium species, anionic palladium nanoclusters [PdnR(DE)n]−, (n=2, 4, 6; DE=diene) were also observed. At short reaction times, the dinuclear complexes usually predominated, whereas at longer times the tetra‐ and hexanuclear clusters became relatively more abundant. In parallel, the formation of palladium black pointed to continued aggregation processes. Thus, the present study directly shows dynamic behavior of the palladium/diene catalyst system and degradation of the active catalyst with increasing reaction time.

The electron‐poor palladium(0) complex L3Pd (L=tris[3,5‐bis(trifluoromethyl)phenyl]phosphine) reacts with Grignard reagents RMgX and organolithium compounds RLi via transmetalation to furnish the anionic organopalladates [L2PdR]−, as shown by negative‐ion mode electrospray‐ionization mass spectrometry. These palladates undergo oxidative additions of organyl halides R′X (or related SN2‐type reactions) followed by further transmetalation. Gas‐phase fragmentation of the resulting heteroleptic palladate(II) complexes results in the reductive elimination of the cross‐coupling products RR′. This reaction sequence corresponds to a catalytic cycle, in which the order of the elementary steps of transmetalation and oxidative addition is switched relative to that of palladium‐catalyzed cross‐coupling reactions proceeding via neutral intermediates. An attractive feature of the palladate‐based catalytic system is its ability to mediate challenging alkyl–alkyl coupling reactions. However, the poor stability of the phosphine ligand L against decomposition reactions has so far prevented its successful use in practical applications.