Gold‐Mediated CI Bond Activation of Iodobenzene

Robinson, Peter S. D.; Khairallah, George N.; Silva, Gabriel da; Lioe, Hadi; O’Hair, Richard A. J.

doi:10.1002/ange.201108502

Cited by 47 publications

(33 citation statements)

References 39 publications

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“…To probe the gas‐phase Mizoroki–Heck coupling, complex ions [Pd(dppp)(Ar)] + ( 2 ) were mass selected in the ion trap and reacted with dimethylbutadiene (DMB) introduced into the trap by the gas flow of the helium‐background gas 5c. 11b, 12b, 16 The IMRs of all complex ions [Pd(dppp)(Ar)] + ( 2 ) with DMB led exclusively to the formation of isobaric product ions 4 / 4′ with a characteristic mass shift of 82 Da (DMB: C 6 H 10 , ions 4 a and 4 a′ in Figure 1 b). The complex ions 4 represent [Pd(dppp)(aryl–butenyl)] + species formed after DMB carbopalladation.…”

Section: Methodsmentioning

confidence: 99%

Aryl–Phenyl Scrambling in Intermediate Organopalladium Complexes: A Gas‐Phase Study of the Mizoroki–Heck Reaction

Fiebig

Schlörer

Schmalz

et al. 2014

Chemistry A European J

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The intramolecular aryl-phenyl scrambling reaction within palladium-DPPP-aryl complex (DPPP=1,3-bis(diphenylphosphino)propane) ions was analyzed by state-of-the-art tandem MS, including gas-phase ion/molecule reactions. The Mizoroki-Heck cross-coupling reaction was performed in the gas phase, and the intrinsic reactivity of important intermediates could be examined. Moreover, linear free-energy correlations were applied, and a mechanism for the scrambling reaction proceeding via phosphonium cations was assumed.

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Section: Methodsmentioning

confidence: 99%

Aryl–Phenyl Scrambling in Intermediate Organopalladium Complexes: A Gas‐Phase Study of the Mizoroki–Heck Reaction

Fiebig

Schlörer

Schmalz

et al. 2014

Chemistry A European J

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“…[17] Mass spectrometry studies suggest that a transient [L 2 Au 3 ] + ion, where L 2 is a bridging bisphosphine, undergoes oxidative addition with aryl iodides. [18] Cluster complexes featuring the cyclo-Au 3 moiety bonded to tungsten [19] or to main-group elements [20] are known, as are triangular [Au 2 M] clusters. [21] We now report the characterization of a stable [(LAu) 3 ] + complex, where L is the N-heterocyclic carbene (NHC) 1,3bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IDipp).…”

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confidence: 99%

Synthesis of a Trigold Monocation: An Isolobal Analogue of [H₃]⁺

et al. 2012

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The ion [H 3 ] + represents a classic case in molecular orbital theory, the simplest three-center, two-electron bond. [1] The proton affinity of dihydrogen in the gas phase, at 4.4 eV, [2] is nearly equal to the bond enthalpy of H 2 itself. [3] The [H 3 ] + ion has been studied spectroscopically in the laboratory; [4] it has been detected in planetary atmospheres, [5a] and is notably abundant in interstellar space. [5b] The concept of isolobality has been used extensively to draw analogies between [LAu] + and [H] + , [6] and after the discovery of isolable [(LAu) 2 H] + complexes, [7,8] we became interested in the synthesis of an allgold analogue of [H 3 ] + .Complexes of gold(I) with atoms such as oxygen and the heavier chalcogens, nitrogen, and carbon, often exhibit weak but important aurophilic interactions between the d 10 metal centers. [9] Multicenter covalent bonding is observed in formally mixed-valent gold(I)/gold(0) clusters. [10] These include edge-sharing bitetrahedral clusters of the general formula [(LAu) 6 ] 2+ , [11] and tetrahedral clusters of the formula [(LAu) 4 ] 2+ . [12] Clusters such as [(LAu) 6 ] 2+ , (L 6 Au 8 ) 2+ , and [(LAu) 4 ] 2+ , have been synthesized by the reduction of phosphine-supported m 3 -oxo or m 3 -imido cations with carbon monoxide. [13] Whereas gold(II) dimers form covalent goldgold bonds through the interaction of half-filled d-orbitals, [14] the gold-gold bonding in mixed-valent gold(I)/gold(0) clusters [(LAu) n ] x+ arises to an important extent from symmetryadapted combinations of partially filled gold 6 s orbitals. [10b] The interaction of small gold clusters and nanoparticles with O 2 has been studied as a key step in aerobic oxidation catalysis. [15] The [Au 3 ] + -catalyzed oxidation of CO has been studied theoretically, [16] and [Au 3 ] + in the gas phase has been shown to mediate the oxidation of CO by N 2 O. [17] Mass spectrometry studies suggest that a transient [L 2 Au 3 ] + ion, where L 2 is a bridging bisphosphine, undergoes oxidative addition with aryl iodides. [18] Cluster complexes featuring the cyclo-Au 3 moiety bonded to tungsten [19] or to main-group elements [20] are known, as are triangular [Au 2 M] clusters. [21] We now report the characterization of a stable [(LAu) 3 ] + complex, where L is the N-heterocyclic carbene (NHC) 1,3bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IDipp). Density functional theory (DFT) lends insight into the bonding among gold centers. Preliminary studies demonstrate sluggish reactivity with oxygen-atom-transfer agents, but facile reactivity with soft electrophiles.Initially, we planned to obtain [(LAu) 3 ] + through the reduction of a corresponding m 3 -oxo complex [(LAu) 3 O] + . A wide range of phosphorus-based donor ligands support complexes of this type. [22] Our efforts to obtain an analogous NHC-supported species by the established routes gave rise to mixtures of products, including the hydroxide-bridged digold cation [(LAu) 2 OH] + . [23] Reasoning that the formation of strong silicon-heteroatom bonds co...

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“…[13] For oxidative addition reactions, however, comparatively little and generally only indirect information has been gained. [14,15] Aside from the work of Bachmann et al on s(SÀS) bond activation, direct spectroscopic and crystallographic evidence for the intramolecular oxidative addition of s(Si À Si) bonds was reported by our group. [16] In this project, we took advantage of chelating assistance with a phosphine to pre-orientate the s(SiÀSi) bond and to stabilize the ensuing oxidative addition product.…”

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confidence: 99%

Direct Evidence for Intermolecular Oxidative Addition of σ(SiSi) Bonds to Gold

et al. 2013

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Oxidative addition plays a major role in transition-metal catalysis, but this elementary step remains very elusive in gold chemistry. It is now revealed that in the presence of GaCl3, phosphine gold chlorides promote the oxidative addition of disilanes at low temperature. The ensuing bis(silyl) gold(III) complexes were characterized by quantitative (31)P and (29)Si NMR spectroscopy. Their structures (distorted Y shape) and the reaction profile of σ(Si-Si) bond activation were analyzed by DFT calculations. These results provide evidence for the intermolecular oxidative addition of σ(Si-Si) bonds to gold and open promising perspectives for the development of new gold-catalyzed redox transformations.

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Gold‐Mediated CI Bond Activation of Iodobenzene

Cited by 47 publications

References 39 publications

Aryl–Phenyl Scrambling in Intermediate Organopalladium Complexes: A Gas‐Phase Study of the Mizoroki–Heck Reaction

Aryl–Phenyl Scrambling in Intermediate Organopalladium Complexes: A Gas‐Phase Study of the Mizoroki–Heck Reaction

Synthesis of a Trigold Monocation: An Isolobal Analogue of [H₃]⁺

Direct Evidence for Intermolecular Oxidative Addition of σ(SiSi) Bonds to Gold

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Gold‐Mediated CI Bond Activation of Iodobenzene

Cited by 47 publications

References 39 publications

Aryl–Phenyl Scrambling in Intermediate Organopalladium Complexes: A Gas‐Phase Study of the Mizoroki–Heck Reaction

Aryl–Phenyl Scrambling in Intermediate Organopalladium Complexes: A Gas‐Phase Study of the Mizoroki–Heck Reaction

Synthesis of a Trigold Monocation: An Isolobal Analogue of [H3]+

Direct Evidence for Intermolecular Oxidative Addition of σ(SiSi) Bonds to Gold

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Synthesis of a Trigold Monocation: An Isolobal Analogue of [H₃]⁺