Copper-alumanyl complexes, [LCu-Al(SiN Dipp )], where L = carbene = NHC iPr (N,N'-di-isopropyl-4,5-dimethyl-2-ylidene) and Me2 CAAC (1-(2,6-di-isopropylphenyl)-3,3,5,5-tetramethyl-pyrrolidin-2-ylidene) and featuring unsupported Al-Cu bonds, have been prepared. Divergent reactivity observed with carbodiimides and CO 2 implies an ambiphilicity in the Cu-Al interaction that is dependent on the identity of the carbene co-ligand.

Ambiphilic Al-Cu Bonding.

A gold-aluminyl complex has been recently reported to feature an unconventional gold nucleophilic center, which was revealed through reactivity with carbon dioxide leading to the Au-CO2 coordination mode. In this work, we computationally investigate the reaction mechanism, which is found to be cooperative, with the gold-aluminum bond being the actual nucleophile and Al also behaving as electrophile. The Au-Al bond is shown to be mainly of an electron-sharing nature, with the two metal fragments displaying a diradical-like reactivity with CO2.

Reactivity of a Gold-Aluminyl Complex with Carbon Dioxide: A Nucleophilic Gold?

Anionic aluminum(I) anions (“aluminyls”) are the most recent discovery along Group 13 anions, and the understanding of the unconventional reactivity they are able to induce at a coordinated metal site is at an early stage. A striking example is the efficient insertion of carbon dioxide into the Au–Al bond of a gold–aluminyl complex. The reaction occurs via a cooperative mechanism, with the gold–aluminum bond being the actual nucleophile and the Al site also behaving as an electrophile. In the complex, the Au–Al bond has been shown to be mainly of an electron-sharing nature, with the two metal fragments displaying a diradical-like reactivity with CO2. In this work, the analogous reactivity with isostructural Au–X complexes (X = Al, Ga, and In) is computationally explored. We demonstrate that a kinetically and thermodynamically favorable reactivity with CO2 may only be expected for the gold–aluminyl complex. The Au–Al bond nature, which features the most (nonpolar) electron-sharing character among the Group 13 anions analyzed here, is responsible for its highest efficiency. The radical-like reactivity appears to be a key ingredient to stabilize the CO2 insertion product. This investigation elucidates the special role of Al in these hetero-binuclear compounds, providing new insights into the peculiar electronic structure of aluminyls, which may help for the rational control of their unprecedented reactivity toward carbon dioxide.

https://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.1c03579

What Singles out Aluminyl Anions? A Comparative Computational Study of the Carbon Dioxide Insertion Reaction in Gold–Aluminyl, −Gallyl, and −Indyl Complexes

The unconventional carbon dioxide insertion reaction of a gold-aluminyl [tBu3PAuAl(NON)] complex has been recently shown to be related to the electron-sharing character of the Au–Al bond that acts as a nucleophile and stabilizes the insertion product through a radical-like behavior. Since a gold-diarylboryl [IPrAuB(o-tol)2] complex with similar reactivity features has been recently reported, in this work we computationally investigate the reaction of carbon dioxide with [LAuX] (L = phosphine, N-heterocyclic carbene (NHC); X = Al(NON), B(o-tol)2) complexes to get insights into the Al/B anionic and gold ancillary ligand effects on the Au–Al/B bond nature, electronic structure, and reactivity of these compounds. We demonstrate that the Au–Al and Au–B bonds possess a similar electron-sharing nature, with diarylboryl complexes displaying a slightly more polarized bond as Au(δ+)–B(δ–). This feature reduces the radical-like reactivity toward CO2, and the Al/B anionic ligand effect is found to favor aluminyls over boryls, despite the greater oxophilicity of B. Remarkably, the ancillary ligand of gold has a negligible electronic trans effect on the Au–X bond and only a minor impact on the formation of the insertion product, which is slightly more stable with carbene ligands. Surprisingly, we find that the modification of the steric hindrance at the carbene site may exert a sizable control over the reaction, with more sterically hindered ligands thermodynamically disfavoring the formation of the CO2 insertion product.

Gold-Aluminyl and Gold-Diarylboryl Complexes: Bonding and Reactivity with Carbon Dioxide

This manuscript describes the first example of an alkyne insertion to the Au-B bond of a di(o-tolyl)borylgold complex to afford a cis-2-borylalkenylgold complex, and its isomerization to result in interchanging substituents on the alkenyl carbon atom and the boron atom. The former reaction is the first example of an alkyne insertion to a Au-B bond. In the latter reaction, the regiochemistry of the isomerized alkenylgold products varied depending on the substituents. DFT calculations revealed the formation of gold alkynylborates as a common intermediate via a "retro-1,2-metalate shift", which can be considered as an anti-β-carbon/silicon elimination, and identified a subsequent 1,2-metalate shift as the regiochemistry-determining step. Relative energies of the transition states to each isomer and natural-bond-orbital (NBO) analyses were used to clearly rationalize the regiochemistry of the products.

Isomerization of a cis-(2-Borylalkenyl)gold Complex via a 'Retro-1,2-Metalate Shift': Cleavage of a C–C/C–Si Bond trans to a C–Au Bond

A di(o-tolyl)borylgold complex was synthesized via the metathesis reaction of a gold alkoxide with tetra(o-tolyl)diborane(4). The resulting diarylborylgold complex exhibited a Lewis acidic boron center and a characteristic visible absorption that arises from its HOMO–LUMO excitation, which is narrower than that of a previously reported dioxyborylgold complex. The diarylborylgold complex reacted with isocyanide in a stepwise fashion to afford single- and double-insertion products and a C–C coupled product. Reactions of this diarylborylgold complex with CO/N double bond species furnished addition products under concomitant formation of Au–C and B–O/N bonds, which suggests nucleophilic reactivity of the gold metal center. DFT calculations provided details of the underlying reaction mechanism, which involves an initial coordination of the CO/N bond to the boron vacant p-orbital of the diarylboryl ligand followed by a migration of the gold atom from the tetracoordinate sp3-hybridized boron center, which is analogous to the reactivity of the conventional sp3-hybridized borate species. The DFT calculations also suggested a stepwise mechanism for the reaction of this diarylborylgold complex with isocyanide, which afforded three different reaction products depending on the applied reaction conditions.

/pdf/nucleophilic-reactivity-of-the-gold-atom-in-a-5bgbvcfewl.pdf

Nucleophilic reactivity of the gold atom in a diarylborylgold(I) complex toward polar multiple bonds

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Isomerization of a cis-(2-Borylalkenyl)gold Complex via a 'Retro-1,2-Metalate Shift': Cleavage of a C–C/C–Si Bond trans to a C–Au Bond

Nucleophilic reactivity of the gold atom in a diarylborylgold(I) complex toward polar multiple bonds