Lewis Acid-Assisted C(sp3)-C(sp3) Reductive Elimination at Gold.

The phosphine-borane iPr2P(o-C6H4)BFxyl2 (Fxyl = 3,5-(F3C)2C6H3) 1-Fxyl was found to promote the reductive elimination of ethane from [AuMe2(µ-Cl)]2. Nuclear magnetic resonance monitoring revealed the intermediate formation of the (1-Fxyl)AuMe2Cl complex. Density functional theory calculations identified a zwitterionic path as the lowest energy profile, with an overall activation barrier more than 10 kcal/mol lower than without borane assistance. The Lewis acid moiety first abstracts the chloride to generate a zwitterionic Au(III) complex, which then readily undergoes C(sp3)-C(sp3) coupling. The chloride is finally transferred back from boron to gold. The electronic features of this Lewis-assisted reductive elimination at gold have been deciphered by intrinsic bond orbital analyses. Sufficient Lewis acidity of boron is required for the ambiphilic ligand to trigger the C(sp3)-C(sp3) coupling, as shown by complementary studies with two other phosphine-boranes, and the addition of chlorides slows down the reductive elimination of ethane.

Base-Triggered Oxidative Addition to Gold.

The coordination of secondary phosphine oxides (SPO) was shown to efficiently promote the activation of C(sp2 )-I bonds by gold, as long as a base is added (NEt3 , K2 CO3 ). These transformations stand as a new type of chelation-assisted oxidative addition to gold. The role of the base and the influence of the electronic properties of the P-ligand were analyzed computationally. Accordingly, the oxidative addition was found to be dominated by Au→(Ar-I) backdonation. In this case, gold behaves similarly to palladium, suggesting that the inverse electron flow reported previously (with prevailing (Ar-I)→Au donation, resulting in faster reactions of electron-enriched substrates) is a specific feature of electron-deficient cationic gold(I) complexes. The reaction gives straightforward access to (P=O,C)-cyclometallated Au(III) complexes. The possibility to chemically derivatize the SPO moiety at Au(III) was substantiated by protonation and silylation reactions.

σ-Cyclopropyl to π-Allyl Rearrangement at AuIII.

The possibility for AuIII σ-cyclopropyl complexes to undergo ring-opening and give π-allyl complexes was interrogated. The transformation was first evidenced within (P,C)-cyclometalated complexes, it occurs within hours at -50 °C. It was then generalized to other ancillary ligands. With (N,C)-cyclometalated complexes, the rearrangement occurs at room temperature while it proceeds already at -80 °C with a dicationic (P,N)-chelated complex. Density Functional Theory (DFT) calculations shed light on the mechanism of the transformation, a disrotatory electrocyclic ring-opening. Intrinsic Bond Orbital (IBO) analysis along the reaction profile shows the cleavage of the distal σ(CC) bond to give a π-bonded allyl moiety. Careful inspection of the structure and bonding of cationic σ-cyclopropyl complexes support the possible existence of C-C agostic interactions at AuIII .

Three-centre electron sharing indices (3c-ESIs) as a tool to differentiate among (an)agostic interactions and hydrogen bonds in transition metal complexes.

The agostic bond plays an important role in chemistry, not only in transition metal chemistry but also in main group chemistry. In some complexes with M⋯H-X (X = C, N) interactions, differentiation among agostic, anagostic, and hydrogen bonds is challenging. Here we propose the use of three-centre electron sharing indices to classify M⋯H-X (X = C, N) interactions.

Nucleophilic Addition to π-Allyl Gold(III) Complexes: Evidence for Direct and Undirect Paths.

π-Allyl complexes play a prominent role in organometallic chemistry and have attracted considerable attention, in particular the π-allyl Pd(II) complexes which are key intermediates in the Tsuji-Trost allylic substitution reaction. Despite the huge interest in π-complexes of gold, π-allyl Au(III) complexes were only authenticated very recently. Herein, we report the reactivity of (P,C)-cyclometalated Au(III) π-allyl complexes toward ß-diketo enolates. Behind an apparently trivial outcome, i.e. the formation of the corresponding allylation products, meticulous NMR studies combined with DFT calculations revealed a complex and rich mechanistic picture. Nucleophilic attack can occur at the central and terminal positions of the π-allyl as well as the metal itself. All paths are observed and are actually competitive, whereas addition to the terminal positions largely prevails for Pd(II). Auracyclobutanes and π-alkene Au(I) complexes were authenticated spectroscopically and crystallographically, and Au(III) σ-allyl complexes were unambiguously characterized by multinuclear NMR spectroscopy. Nucleophilic additions to the central position of the π-allyl and to gold are reversible. Over time, the auracyclobutanes and the Au(III) σ-allyl complexes evolve into the π-alkene Au(I) complexes and release the C-allylation products. The relevance of auracyclobutanes in gold-mediated cyclopropanation was demonstrated by inducing C-C coupling with iodine. The molecular orbitals of the π-allyl Au(III) complexes were analyzed in-depth, and the reaction profiles for the addition of ß-diketo enolates were thoroughly studied by DFT. Special attention was devoted to the regioselectivity of the nucleophilic attack, but C-C coupling to give the allylation products was also considered to give a complete picture of the reaction progress.

Fluorosilane Activation by Pd/Ni→Si-F→Lewis Acid Interaction: An Entry to Catalytic Sila-Negishi Coupling.

A new mode of bond activation involving M→Z interactions is disclosed. Coordination to transition metals as σ-acceptor ligands was found to enable the activation of fluorosilanes, opening the way to the first transition-metal-catalyzed Si-F bond activation. Using phosphines as directing groups, sila-Negishi couplings were developed by combining Pd and Ni complexes with external Lewis acids such as MgBr2. Several key catalytic intermediates have been authenticated spectroscopically and crystallographically. Combined with DFT calculations, all data support cooperative activation of the fluorosilane via Pd/Ni→Si-F→Lewis acid interaction with conversion of the Z-type fluorosilane ligand into an X-type silyl moiety.

Impact of C=C/B-N Replacement on the Diels-Alder Reactivity of Curved Polycyclic Aromatic Hydrocarbons.

The influence of the replacement of C=C bonds by isoelectronic B-N moieties on the reactivity of π-curved polycyclic aromatic hydrocarbons has been computationally explored by means of density functional theory calculations. To this end, we selected the Diels-Alder cycloaddition reactions of the parent corannulene and its BN-doped counterparts with either cyclopentadiene or maleic anhydride. In addition, the analogous reactions involving larger buckybowls, such as BN-hemifullerene, BN-circumtrindene, and BN-fullerene, have been also considered. It has been found that whereas corannulene behaves as a dienophile, its BN counterpart better acts as a diene. In contrast, the larger BN-curved systems cannot be used as dienes in Diels-Alder reactions, but undergo facile (i.e., low barrier) cycloaddition reactions with cyclopentadiene. The observed trends in reactivity, which cannot be directly explained by using typical frontier molecular orbital arguments, are quantitatively described in detail by means of state-of-the-art computational methods, namely the activation strain model of reactivity combined with the energy decomposition analysis method. The results of our calculations highlight the crucial role of the curvature of the system on the reactivity and its influence on the strength of the orbital interactions between the deformed reactants during their transformations.

Factors Controlling the Reactivity of Strained-Alkyne Embedded Cycloparaphenylenes.

The factors controlling the reactivity of the strained-alkyne embedded cycloparaphenylenes have been computationally explored by means of Density Functional Theory calculations. To this end, the Diels-Alder cycloaddition reaction involving cyclopentadiene and these macrocyclic systems has been selected in order to understand the influence of the strained nature of the alkyne in their structures as well as the size of the system on their reactivity. It is found that the cycloaddition reactions involving those macrocycles having more strained alkynes not only are more exothermic and exhibit lower activation barriers but also are associated with earlier transition states. The combination of the Activation Strain Model of reactivity and the Energy Decomposition Analysis method suggests that the enhanced reactivity of bent alkynes, as compared to linear C≡C triple bonds, finds its origin not only in the lower deformation energy required to adopt the corresponding transition state structure but also in the stronger interaction energy between the deformed reactants.

Rationalizing the Regioselectivity of the Diels-Alder Biscycloaddition of Fullerenes.

The physical factors governing the regioselectivity of the double functionalization of fullerenes have been explored by means of density functional theory calculations. To this end, the second Diels-Alder cycloaddition reactions involving 1,3-butadiene and the parent C60 fullerene as well as the ion-encapsulated system Li+@C60 have been selected. In agreement with previous experimental findings on related processes, it is found that the cycloaddition reaction, involving either C60 or Li+@C60, occurs selectively at specific [6,6]-bonds. The combination of the activation strain model of reactivity and the energy decomposition analysis methods has been applied to gain a quantitative understanding into the markedly different reactivity of the available [6,6]-bonds leading to the observed regioselectivity in the transformation.

Influence of the charge on the reactivity of azafullerenes.

The influence of the charge on the Diels-Alder reactivity of azafullerenes (C59N+ and C59N-) has been computationally explored by means of density functional theory calculations. In addition, the regioselectivity of the process has been investigated and compared to the analogous cycloaddition reaction involving the parent neutral azahydro[60]fullerene C59NH. It is found that the [4+2]-cycloaddition reaction between C59N+ and cyclopentadiene, which occurs concertedly through a synchronous transition state, proceeds with a lower activation barrier and is more exothermic than the analogous process involving C59NH. In contrast, the anionic C59N- counterpart is clearly less reactive. This reactivity trend is quantitatively analyzed in detail by means of the activation strain model of reactivity in combination with the energy decomposition analysis method. It is found that the frontier molecular orbital interactions are not responsible for the observed reactivity trend but the Pauli repulsion between closed-shells mainly governs the transformation.

Influence of the Transition-Metal Fragment on the Reactivity of Metallaanthracenes.

The influence of the nature of the transition-metal fragment on the Diels-Alder reactivity of metallaanthracenes has been explored computationally within the Density Functional Theory framework. It is found that the cycloaddition reactions with maleic anhydride become kinetically less favored for those processes involving metallaanthracenes compared with the analogous reaction involving the parent anthracene. The origins of this reduction in the Diels-Alder reactivity have been quantitatively analyzed in detail by using the activation strain model of reactivity in combination with the energy decomposition analysis method. In general, the transition-metal fragment makes the interaction energy between the reactants significantly lower, particularly at the transition state region, which is translated into a higher activation barrier. In addition, the influence of the aromaticity strength of the metallabenzene present in the considered metallaanthracenes on the barriers of the cycloaddition reactions has also been assessed.

Understanding the Reactivity of Ion-Encapsulated Fullerenes.

The influence of the encapsulation of an ion inside the C60 fullerene cage on its exohedral reactivity was explored by means of DFT calculations. To this end, the Diels-Alder reaction between 1,3-cyclohexadiene and M@C60 (M=Li+ , Na+ , K+ , Be2+ , Mg2+ , Al3+ , and Cl- ) was studied and compared to the analogous process involving the parent C60 fullerene. A significant enhancement of the Diels-Alder reactivity is found for systems having an endohedral cation, whereas a clear decrease in reactivity is observed when an anion is encapsulated in the C60 cage. The origins of this reactivity trend were quantitatively analyzed in detail by using the activation strain model of reactivity in combination with energy decomposition analysis.

Factors Governing the Diels-Alder Reactivity of (2,7)Pyrenophanes.

The physical factors governing the Diels-Alder reactivity of (2,7)pyrenophanes have been computationally explored using state-of-the-art Density Functional Theory calculations. It is found that the [4 + 2]-cycloaddition reactions between these cyclophanes and tetracyanoethylene, which occur concertedly through highly asynchronous transition states, proceed with lower activation barriers and are more exothermic than the analogous process involving the parent planar pyrene. The influence of the bent equilibrium geometry of the pyrenophane as a function of the length of the bridge as well as the nature of the tether on the transformation are analyzed in detail. By means of the Activation Strain Model of reactivity and the Energy Decomposition Analysis methods, a detailed quantitative understanding of the reactivity of this particular family of cyclophanes is presented.

Predicting and Understanding the Reactivity of Aza[60]fullerenes.

The Diels-Alder reactivity of C59NH azafullerene has been explored computationally. The regioselectivity of the process and the factors controlling the reduced reactivity of this system with respect to the parent C60 fullerene have been analyzed in detail by using the activation strain model of reactivity and the energy decomposition analysis method. It is found that the presence of the nitrogen atom and the CH fragment in the fullerene reduces the interaction between the deformed reactants along the entire reaction coordinate.

Understanding the Oxidative Addition of σ-Bonds to Group†13 Compounds.

The oxidative addition reaction of X-H σ-bonds to Group 13 (E=Al, Ga, In) containing compounds has been computationally explored within the density functional theory framework. These reactions, which proceed concertedly involving the E(I) →E(III) oxidation, are exothermic and associated with relatively low activation barriers. In addition, the following trends in reactivity are found: (i) the activation barriers are lower for the X-H bonds involving the heavier element in the same group (ΔE(≠) : C>Si; N>P; O>S), (ii) the process becomes kinetically more favorable in going from left to right in the same period (ΔE(≠) : C>N>O; Si≈P>S), and (iii) the activation barrier systematically increases when heavier Group 13 elements are involved in the transformation (ΔE(≠) : Al

Understanding the Reactivity of Planar Polycyclic Aromatic Hydrocarbons: Towards the Graphene Limit.

The Diels-Alder reactivity of maleic anhydride towards the bay regions of planar polycyclic aromatic hydrocarbons was explored computationally in the DFT framework. The process becomes more and more exothermic and the associated activation barriers become lower and lower when the size of the system increases. This enhanced reactivity follows an exponential behavior that reaches its maximum for systems having 18-20 benzenoid rings in their structures. This peculiar behavior was analyzed in detail by using the activation strain model of reactivity in combination with energy decomposition analysis. The influence of the change in the aromaticity of the polycyclic compound during the process on the respective activation barriers was also studied.

Reactivity and Selectivity of Bowl-Shaped Polycyclic Aromatic Hydrocarbons: Relationship to C60.

The Diels-Alder reactivity of different bowl-shaped polycyclic aromatic hydrocarbons (namely, corannulene, cyclopentacorannulene, diindenochrysene, hemifullerene, and circumtrindene) has been explored computationally within the DFT framework. To this end, both the increase in reactivity with the size of the buckybowl and complete [6,6]-regioselectivity in the process have been analyzed in detail by using the activation strain model of reactivity in combination with the energy decomposition analysis method. These results have been compared with the parent C60 fullerene, which also produces the corresponding [6,6]-cycloadduct exclusively. The behavior of the buckybowls considered herein resembles, in general, that of C60 . Whereas the interaction energy between the deformed reactants along the reaction coordinate mainly controls the regioselectivity of the process, it is the interplay between the activation strain energy and the transition-state interaction that governs the reactivity of the system.

Factors Controlling the Reactivity and Selectivity of the Diels-Alder Reactions Involving 1,2-Azaborines.

The factors controlling the reactivity and endo/exo selectivity of the Diels-Alder reactions involving 1,2-azaborines have been computationally explored within the density functional theory framework. It is found that the AlCl3-catalyzed [4 + 2]-cycloaddition reaction between these dienes and N-methylmaleimide proceeds concertedly and leads almost exclusively to the corresponding endo cycloadduct, which is in good agreement with previous experimental observations. In addition, the effect of the substituent directly attached to the boron atom of the 1,2-azaborine on the process is also analyzed in detail. To this end, the combination of the activation strain model of reactivity and the energy decomposition analysis methods has been applied to gain a quantitative understanding into the origins of the endo selectivity of the process as well as the influence of the boron and nitrogen substituent on the barrier heights of the transformations.

Catechol/o-benzoquinone exchange at gold(iii).

Although gold(iii) chemistry has tremendously progressed in the past 2 decades, gold(iii) catecholate complexes remain extremely scarce and underdeveloped. Upon preparation and full characterization of P^C-cyclometalated gold(iii) complexes, we serendipitously uncovered an intriguing catechol exchange process at gold(iii). Electron-rich catecholates turned out to be readily displaced by electron-poor o-benzoquinones. DFT calculations revealed an original path for this transformation involving two consecutive Single Electron Transfer events between the catecholate and o-benzoquinone moieties while gold maintains its +III oxidation state. This catechol/o-benzoquinone exchange at gold(iii) represents a new path for the exchange of X-type ligands at transition metals.

Formation and reactivity of a unique M⋯C-H interaction stabilized by carborane cages.

Broadening carborane applications has consistently been the goal of chemists in this field. Herein, compared to alkyl or aryl groups, a carborane cage demonstrates an advantage in stabilizing a unique bonding interaction: M⋯C-H interaction. Experimental results and theoretical calculations have revealed the characteristic of this two-center, two-electron bonding interaction, in which the carbon atom in the arene ring provides two electrons to the metal center. The reduced aromaticity of the benzene moiety, long distance between the metal and carbon atom in arene, and the upfield shift of the signal of M⋯C-H in the nuclear magnetic resonance spectrum distinguished this interaction from metal⋯C π interaction and metal-C(H) σ bonds. Control experiments demonstrate the unique electronic effects of carborane in stabilizing the M⋯C-H bonding interaction in organometallic chemistry. Furthermore, the M⋯C-H interaction can convert into C-H bond metallization under acidic conditions or via treatment with t-butyl isocyanide. These findings deepen our understanding regarding the interactions between metal centers and carbon atoms and provide new opportunities for the use of carboranes.