Coinage metal aluminyl complexes: probing regiochemistry and mechanism in the insertion and reduction of carbon dioxide

McManus, Caitilín; Hicks, Jamie; Cui, Xianlu; Zhao, Lili; Frenking, Gernot; Goicoechea, José M.; Aldridge, Simon

doi:10.1039/d1sc04676d

Cited by 51 publications

(76 citation statements)

References 68 publications

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“…Visualization of the vibrational modes associated with the imaginary frequency of TSI′ (−212.5 cm –1 ) indicates (analogous to TSI ) a concerted transition state associated with a vibrational mode involving Au–C, Al–O, and Al–C interactions. We should also mention that in ref ( 11 ), using a different computational protocol, a transition state has been reported which is very similar to that of TSI′ in Figure 3 , consistent with the very flat PES we show here.…”

Section: Resultssupporting

confidence: 91%

“… 13 Notably, examples of molecular gold–gallyl complexes have been also reported in the past 14 , 15 and very recently the silver–gallyl analogue of I (i.e., the [ t Bu 3 PAgGa(NON)] complex) has been characterized. 11 Formally anionic boryls have also been known for years, 16 , 17 and recently, the nucleophilic reactivity of a nonheterocyclic gold–boryl complex toward multiple polar bonds has been reported. 18 Notably, a copper–boryl complex has been reported in the past to catalyze the reduction of CO 2 to CO. 19 , 20 Concerning the heavier analogue, indium, a six-membered heterocyclic indyl anion (i.e., In( Ar NON)] − , Ar NON = [O(SiMe 2 NAr) 2 ] 2– , Ar = 2,6- i Pr 2 C 6 H 3 ) has also been recently reported, 21 bearing the same heterocyclic backbone of the diamido aluminyl [Al( Si NON)] − ( Si NON = [O(SiMe 2 NDipp) 2 ] 2– , Dipp = 2,6- i Pr 2 C 6 H 3 ).…”

Section: Introductionmentioning

confidence: 99%

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

Sorbelli

Belpassi²,

Belanzoni

2022

Inorg. Chem.

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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 CO 2 . 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 CO 2 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 CO 2 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.

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Section: Resultssupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

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

Sorbelli

Belpassi²,

Belanzoni

2022

Inorg. Chem.

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“… 8 Conversely, the same reactivity has been explored with the phosphine-copper [ t Bu 3 PCuAl(NON)] complex and the isolation of a II -type insertion product was not possible due to its extremely fast evolution to a copper-carbonate complex (resulting from CO extrusion). 9 These findings suggest that the gold ancillary ligand may have a role in the reactivity that, due to the unprecedented gold chemistry displayed by these heterobinuclear complexes, needs to be yet undisclosed.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2022

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The unconventional carbon dioxide insertion reaction of a gold-aluminyl [ t Bu 3 PAuAl(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 CO 2 , 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 CO 2 insertion product.

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“…[3j] To date,t he solid-state structural authentication of terminal Cu-alumanyl complexes is limited to LCuAl(SiN Dipp )( L= N,N'-diisopropyl-4,5-dimethyl-2-ylidene and (1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethyl-pyrrolidin-2-ylidene) [13] and K[Cu[Al(NON)] 2 ]. [36] These species were formed by as alt metathesis reaction of the corresponding potassium aluminyl compound with al igand-stabilized copper halide.Itisimportant to note that the facile synthesis of 8 showcases an ew avenue to terminal alumanyl complexes that are extremely rare and otherwise difficult to prepare. [4g,j, 12, 13, 36, 37] Themechanism of the formation of 8 was probed via DFT calculations (SMD-M06-2X/def2-TZVP//M06-2X/def2-SVP) (Figure S42).…”

Section: Methodsmentioning

confidence: 99%

A Free Aluminylene with Diverse σ‐Donating and Doubly σ/π‐Accepting Ligand Features for Transition Metals**

Liu

Zhang

2021

Angewandte Chemie

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We report herein the synthesis,characterization, and coordination chemistry of af ree N-aluminylene,n amely ac arbazolylaluminylene 2b.T his species is prepared via ar eduction reaction of the corresponding carbazolyl aluminium diiodide.T he coordination behavior of 2b towards transition metal centers (W,C r) is shown to affordaseries of novel aluminylene complexes 3-6 with diverse coordination modes.W edemonstrate that the tri-active ambiphilic Al center in 2b can behave as:1 .as-donating and doubly p-accepting ligand;2 .a s-donating, s-accepting and p-accepting ligand; and 3. a s-donating and doubly s-accepting ligand. Additionally,w es how ligand exchange at the aluminylene center providing access to the modulation of electronic properties of transition metals without changing the coordinated atoms. Investigations of 2b with IDippCuCl (IDipp = 1,3-bis(2,6diisopropylphenyl)imidazol-2-ylidene) show an unprecedented aluminylene-alumanyl transformation leading to ar are terminal Cu-alumanyl complex 8.The electronic structures of such complexes and the mechanism of the aluminylenealumanyl transformation are investigated through density functional theory (DFT) calculations.[**] Aprevious version of this manuscript has been deposited on apreprint server (https://chemrxiv.org/engage/chemrxiv/articledetails/61205bc21d1cc23402c90876).

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Coinage metal aluminyl complexes: probing regiochemistry and mechanism in the insertion and reduction of carbon dioxide

Abstract: The synthesis of coinage metal aluminyl complexes, featuring M–Al covalent bonds, is reported via a salt metathesis approach employing an anionic Al(I) (‘aluminyl’) nucleophile and group 11 electrophiles. This approach...

Cited by 51 publications

References 68 publications

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

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

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

A Free Aluminylene with Diverse σ‐Donating and Doubly σ/π‐Accepting Ligand Features for Transition Metals**

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