Alkyne insertion into Cu–Al bonds and selective functionalization to form copper acyl compounds

McManus, Caitilín; Crumpton, Agamemnon E; Aldridge, Simon

doi:10.1039/d2cc02578g

Cited by 17 publications

(19 citation statements)

References 32 publications

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“… Sketched stationary point structures along the paths of Figure 1 with selected interatomic distances (Å) and bond angles (°). Values in parentheses refer to experimentally available data taken from ref ( 9 ). …”

Section: Resultsmentioning

confidence: 99%

“…The syn dimetallated alkenes (9-Cu, 11-Cu) can give a selective insertion of CO leading to the formation of copper acyl compounds. 9 Strictly related gold silyl 10,11 and boryl 12 complexes have been also experimentally reported to insert alkynes into Au−Si and Au−B bonds. Amgoune and Bourissou reported that alkynes can be activated via insertion into the Au−Si bond of the gold silyl (R 3 P)AuSiR'Ph .…”

Section: ■ Introductionmentioning

confidence: 99%

“…5 More recently, internal alkyne insertion into the Cu−Al bond of the copper−aluminyl complex 3-Cu has been experimentally reported, producing (aluminylalkenyl)copper compounds which possess different reactivity at the two derived M−C functions. 9 Complex 3-Cu is able to control the nature of the formed (syn or anti) dimetallated alkenes, with syn isomers accessible through a kinetic control with high selectivity and anti isomers isolable through a thermodynamic control (Scheme 2). The syn dimetallated alkenes (9-Cu, 11-Cu) can give a selective insertion of CO leading to the formation of copper acyl compounds.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Complex 3-Cu is able to control the nature of the formed ( syn or anti ) dimetallated alkenes, with syn isomers accessible through a kinetic control with high selectivity and anti isomers isolable through a thermodynamic control (Scheme ). The syn dimetallated alkenes ( 9-Cu , 11-Cu ) can give a selective insertion of CO leading to the formation of copper acyl compounds …”

Section: Introductionmentioning

confidence: 99%

“…The syn dimetallated alkenes ( 9-Cu , 11-Cu ) can give a selective insertion of CO leading to the formation of copper acyl compounds. 9 …”

Section: Introductionmentioning

confidence: 99%

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Mechanistic Study of Alkyne Insertion into Cu–Al and Au–Al Bonds: A Paradigm Shift for Coinage Metal Chemistry

Sorbelli

Belpassi²,

Belanzoni

2022

Inorg. Chem.

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In this work, the mechanism of the insertion reaction of 3-hexyne into Cu−Al and Au−Al bonds in M−aluminyl (M = Cu, Au) complexes is computationally elucidated. The mechanism is found to be radical-like, with the Cu−Al and Au−Al bonds acting as nucleophiles toward the alkyne, and predicts a less efficient reactivity for the gold−aluminyl complex. The proposed mechanism well rationalizes the kinetic (or thermodynamic) control on the formation of the syn (or anti) insertion product into the Cu−Al bond (i.e., dimetallated alkene) which has been recently reported. A comparative analysis of the electronic structure reveals that the reduced reactivity at the gold site�usually showing higher efficiency than copper as a "standard" electrophile in alkyne activation�arises from a common feature, i.e., the highly stable 6s Au orbital. The relativistic lowering of the 6s orbital, making it more suitable for accepting electron density and thus enhancing the electrophilicity of gold complexes, in the gold−aluminyl system is responsible for a less nucleophilic Au−Al bond and, consequently, a less efficient alkyne insertion. These findings demonstrate that the unconventional electronic structure and the electron-sharing nature of the M−Al bond induce a paradigm shift in the properties of coinage metal complexes. In particular, the peculiar radical-like reactivity, previously shown also with carbon dioxide, suggests that these complexes might efficiently insert/activate other small molecules, opening new and unexplored paths for their reactivity.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…The syn dimetallated alkenes ( 9-Cu , 11-Cu ) can give a selective insertion of CO leading to the formation of copper acyl compounds. 9 …”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Mechanistic Study of Alkyne Insertion into Cu–Al and Au–Al Bonds: A Paradigm Shift for Coinage Metal Chemistry

Sorbelli

Belpassi²,

Belanzoni

2022

Inorg. Chem.

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Mercury‐Group 13 Metal Covalent Bonds: A Systematic Comparison of Aluminyl, Gallyl and Indyl Metallo‐ligands

Griffin,

Ellwanger,

Crumpton

et al. 2024

Angewandte Chemie

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Bimetallic compounds containing direct metal‐group 13 element bonds have been shown to display unprecedented patterns of cooperative reactivity towards small molecules, which can be influenced by the identity of the group 13 element. In this context, we present here a systematic appraisal of group 13 metallo‐ligands of the type [(NON)E]‐ (NON = 4,5‐bis(2,6‐diisopropylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene) for E = Al, Ga and In, through a comparison of structural and spectroscopic parameters associated with the trans L or X ligands in linear d10 complexes of the types LM{E(NON)} and XM'{E(NON)}. These studies are facilitated by convenient syntheses (from the In(I) precursor, InCp) of the potassium indyl species [{K(NON)In}·KCp]n (1) and [(18‐crown‐6)2K2Cp] [(NON)In] (1'), and lead to the first structural characterisation of Ag–In and Hg–E (E = Al, In) covalent bonds. The resulting structural, spectroscopic and quantum chemical probes of Ag/Hg complexes are consistent with markedly stronger sigma‐donor capabilities of the aluminyl ligand, [(NON)Al]‐, over its gallium and indium counterparts.

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Mercury‐Group 13 Metal Covalent Bonds: A Systematic Comparison of Aluminyl, Gallyl and Indyl Metallo‐ligands

Griffin,

Ellwanger,

Crumpton

et al. 2024

Angew Chem Int Ed

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Alkyne insertion into Cu–Al bonds and selective functionalization to form copper acyl compounds

Abstract: We report on the insertion of alkynes into heterometallic M–M' bonds, producing (aluminylalkenyl)copper compounds which possess differential reactivity at the two derived M–C functions. Uniquely, this system is capable of...

Cited by 17 publications

References 32 publications

Mechanistic Study of Alkyne Insertion into Cu–Al and Au–Al Bonds: A Paradigm Shift for Coinage Metal Chemistry

Mechanistic Study of Alkyne Insertion into Cu–Al and Au–Al Bonds: A Paradigm Shift for Coinage Metal Chemistry

Mercury‐Group 13 Metal Covalent Bonds: A Systematic Comparison of Aluminyl, Gallyl and Indyl Metallo‐ligands

Mercury‐Group 13 Metal Covalent Bonds: A Systematic Comparison of Aluminyl, Gallyl and Indyl Metallo‐ligands

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