Selectivity in C–Cl bond activation of dichloroarenes by photogenerated Cp*Re(CO)<sub>2</sub>: combined experimental and DFT studies

Aballay, Alvaro; Clot, Eric; Eisenstein, Odile; Garland, Marı́a Teresa; Godoy, Fernando; Klahn, A. Hugo; Muñoz, Juan Carlos; Oelckers, Beatriz

doi:10.1039/b410265g

Cited by 11 publications

(12 citation statements)

References 43 publications

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“…3,4 That is by direct photolysis of Cp*Re(CO) 3 (l = 350 nm, 6 h) in a saturated hexane solution of 2-bromo-1,4-dichlorobenzene at room temperature. Much longer irradiation times produced significant amounts of the dibromo complex Cp*Re(CO) 2 -was inferred from the presence of two CO absorption bands in the 1850-1740 cm -1 region of the IR spectra.…”

Section: Resultsmentioning

confidence: 99%

“…1,2,4,5-Cl 4 C 6 H 2 , 1,2,4-Cl 3 C 6 H 3 , 1,4-Cl 2 C 6 H 4 , 1,3-Cl 2 C 6 H 4 , hydrogen chloride in diethyl ether 1.0 M, superhydride solution in THF 1.0 M (Aldrich) were used as received. Cp*Re(CO) 3 and Cp*Re(CO) 2 N 2 were synthesized following literature procedures. 11,17 Photochemical reactions were carried out at 350 nm with a Rayonet RPR 100 photoreactor in quartz tubes.…”

Section: General Methodsmentioning

confidence: 99%

“…For complex 2b the 1 H NMR spectrum exhibited one set of three signals which reveal the unsymmetrical h Finally, we consider important to point out that like many other η 2 -arenes coordinated to metal fragments, the chlorobenzene ligands in complexes 2 can be easily displaced by other two electron donor ligands, as was evidenced by the reaction of 2a and 2d with CO and PMe 3 with formation of the known complexes Cp*Re(CO) 3 and Cp*Re(CO) 2 (PMe 3 ) respectively.…”

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confidence: 99%

“…2 In contrast, the photochemical reaction of Cp*Re(CO) 3 with partially chlorinated arenes lead to the cleavage of C-Cl bond. [3][4][5] Similar result have been found by Leiva and Sutton in the reaction of several dinitrogen complexes Cp*Re(CO)(L)N 2 (L = phosphine and phosphite) with chlorobenzene. 6 As far as we are aware the h 2 -coordination of chloroarenes to rhenium remains elusive.…”

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confidence: 99%

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η²-COORDINATION OF CHLOROBENZENES TO RHENIUM FRAGMENT CpRe(CO)2: CHEMICAL AND PHOTOCHEMICAL SYNTHESES OF CpRe(CO)2(η²-C6H6-nCl n)

Klahn

Morales

Oelckers

et al. 2011

J. Chil. Chem. Soc.

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The complexes Cp*Re(CO) 2 (h 2 -C 6 H 6-n Cl n ), n = 4, (5,6-h 2 -1,2,3,4-C 6 H 2 Cl 4 ) 2a; n = 3, (5,6-h 2 -1,2,4-C 6 H 3 Cl 3 ) 2b; n = 2, (2,3-h 2 -1,4-C 6 H 4 Cl 2 ) 2c and (4,5-h 2 -1,3-C 6 H 4 Cl 2 ) 2d, have been conveniently prepared by two alternative procedures: Directly, by the photochemical reaction of Cp*Re ( C NMR spectroscopy. The 1 H NMR spectra of the two derivatives containing dichlorobenzene (2c and 2d) indicate that a rapid exchange occurs between the hydrogen atoms on the coordinated carbons and those on the non-coordinated carbons.

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Section: Resultsmentioning

confidence: 99%

Section: General Methodsmentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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η²-COORDINATION OF CHLOROBENZENES TO RHENIUM FRAGMENT CpRe(CO)2: CHEMICAL AND PHOTOCHEMICAL SYNTHESES OF CpRe(CO)2(η²-C6H6-nCl n)

Klahn

Morales

Oelckers

et al. 2011

J. Chil. Chem. Soc.

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“…61,65 The variation of the Bond Dissociation Energies (BDE) of the bonds involved is usually invoked to rationalize such selectivity. Nevertheless, BDE calculations are not infallible and can even be redundant in the case of strong catalyst/ ligand interactions.…”

Section: -61mentioning

confidence: 99%

A catalytic route to dibenzodiazepines involving Buchwald–Hartwig coupling: reaction scope and mechanistic consideration

et al. 2015

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We report a new synthetic method for the synthesis of a family of dibenzodiazepines (DBDAs), employing Pd-catalyzed C-N coupling of o-bromoaldimine, with o-bromoaniline as the key step. Eleven DBDAs were prepared, containing electron-withdrawing groups (CN, F, NO 2 ) and electron-donating groups (OMe). The reaction conditions were optimized (catalyst, phosphine, base and solvent) and best results were obtained with Pd(OAc) 2 , SPhos, Cs 2 CO 3 in THF. Due to the ambiguity of the mechanism at hand, various mechanistic studies were performed, that included DFT calculations. The oxidative addition process was studied in detail by DFT, and these studies supported the observed reaction regioselectivity. The adducts formed between the aldimine and the Pd(0) catalyst were calculated to be more stable than the ones formed with the amine, and the barrier for the oxidative addition at the C-Br bond of the aldimine was calculated to be lower than the one at the C-Br bond of the aryl amine. The formation of DBDA over the dibenzoaminopiperidine has been explained in the final cyclization step.

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Syntheses, Structures and Reactivities of [CpTc(CO)₃X]⁺ and [CpRe(CO)₃X]⁺

2008

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Selectivity in C–Cl bond activation of dichloroarenes by photogenerated Cp*Re(CO)₂: combined experimental and DFT studies

Cited by 11 publications

References 43 publications

η²-COORDINATION OF CHLOROBENZENES TO RHENIUM FRAGMENT CpRe(CO)2: CHEMICAL AND PHOTOCHEMICAL SYNTHESES OF CpRe(CO)2(η²-C6H6-nCl n)

η²-COORDINATION OF CHLOROBENZENES TO RHENIUM FRAGMENT CpRe(CO)2: CHEMICAL AND PHOTOCHEMICAL SYNTHESES OF CpRe(CO)2(η²-C6H6-nCl n)

A catalytic route to dibenzodiazepines involving Buchwald–Hartwig coupling: reaction scope and mechanistic consideration

Syntheses, Structures and Reactivities of [CpTc(CO)₃X]⁺ and [CpRe(CO)₃X]⁺

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Selectivity in C–Cl bond activation of dichloroarenes by photogenerated Cp*Re(CO)2: combined experimental and DFT studies

Cited by 11 publications

References 43 publications

η²-COORDINATION OF CHLOROBENZENES TO RHENIUM FRAGMENT Cp*Re(CO)2: CHEMICAL AND PHOTOCHEMICAL SYNTHESES OF Cp*Re(CO)2(η²-C6H6-nCl n)

η²-COORDINATION OF CHLOROBENZENES TO RHENIUM FRAGMENT Cp*Re(CO)2: CHEMICAL AND PHOTOCHEMICAL SYNTHESES OF Cp*Re(CO)2(η²-C6H6-nCl n)

A catalytic route to dibenzodiazepines involving Buchwald–Hartwig coupling: reaction scope and mechanistic consideration

Syntheses, Structures and Reactivities of [CpTc(CO)3X]+ and [CpRe(CO)3X]+

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Selectivity in C–Cl bond activation of dichloroarenes by photogenerated Cp*Re(CO)₂: combined experimental and DFT studies

η²-COORDINATION OF CHLOROBENZENES TO RHENIUM FRAGMENT CpRe(CO)2: CHEMICAL AND PHOTOCHEMICAL SYNTHESES OF CpRe(CO)2(η²-C6H6-nCl n)

η²-COORDINATION OF CHLOROBENZENES TO RHENIUM FRAGMENT CpRe(CO)2: CHEMICAL AND PHOTOCHEMICAL SYNTHESES OF CpRe(CO)2(η²-C6H6-nCl n)

Syntheses, Structures and Reactivities of [CpTc(CO)₃X]⁺ and [CpRe(CO)₃X]⁺