Selective C–Cl Bond Oxidative Addition of Chloroarenes to a POP–Rhodium Complex

Curto, Sheila G.; Esteruelas, Miguel A.; Oliván, Montserrat; Oñate, Enrique; Vélez, Andrea

doi:10.1021/acs.organomet.6b00615

Cited by 36 publications

(26 citation statements)

References 67 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Rhodium pincer complexes have attracted considerable attention for their catalytic activities in the CC coupling reaction of aryl halides . A recent study reported the oxidative addition reaction of several aryl halides to a POP Rh pincer complex ( 1 ), RhH{xant(P i Pr 2 ) 2 }, where xant(P i Pr 2 ) 2 = 9,9‐dimethyl‐4,5‐bis‐ (diisopropyl‐phosphino)xanthene} …”

Section: Methodsmentioning

confidence: 99%

“…The geometry of the stationary points along reaction paths of the various concerted single‐step oxidative addition reactions were optimized at the B3LYP/LACVP** computational level using the Jaguar v8.4 suite . Initial geometry of 1 _PhCl was taken from the experimental X‐ray structure . The thermodynamic stabilities and kinetic quantities were evaluated by calculating the standard Gibbs energy at 298 K as follows:

normalΔ G = E_{0} + ZPE + normalΔΔ G_{0 \to 298 normalK}

…”

Section: Computational Detailsmentioning

confidence: 99%

See 1 more Smart Citation

Density Functional Theory Study on the Oxidative Addition of Chloroarenes to POP Rhodium Complexes

Kim

Ryu

Hwang

2018

Bulletin Korean Chem Soc

View full text Add to dashboard Cite

The carbon-halogen (C-X) bond oxidative addition reaction of an alkyl or aryl halide to the transition metal atom of an organometallic compound is an essential step for producing partially halogenated organic molecules. 1 Partially substituted aromatic molecules have been extensively studied due to their material, pharmaceutical, and agrochemical applications. 2 The oxidative addition reaction of C-X bonds to a metal center is considered the first step of the catalytic cycle that produces partially halogenated molecules. 3 Rhodium pincer complexes have attracted considerable attention for their catalytic activities in the C C coupling reaction of aryl halides. 4 A recent study reported the oxidative addition reaction of several aryl halides to a POP Rh pincer complex (1), RhH{xant (P i Pr 2 ) 2 }, where xant(P i Pr 2 ) 2 = 9,9-dimethyl-4,5-bis-(diisopropyl-phosphino)xanthene}. 5 In the present study, density functional theoretical (DFT) computations of oxidative addition reaction of aryl halides to the POP Rh pincer complex (1) and its closely related compounds ((2) and (3), Scheme 1) were performed using the Jaguar v8.4 suite. 6 The kinetic data of the Gibbs energy of activation and 3-dimensional geometrical characteristics of the reactants, transition states (TSs), and products were examined to understand the nature of the TS and the effects of the substituents of the aromatic molecules and the transition metal complex.The computational level of B3LYP/LACVP** was selected for the reaction because that level of theory has been applied successfully to obtain the thermodynamic and kinetic characteristics of organometallic reactions to transition metal and Al complexes. 2,7 Figure 1 presents the geometrical structures of the initial weakly bound van der Waals (vdW) complexes, transition states (TS), and final oxidation reaction products between (1) (or (3)), and chlorobenzene reaction using B3LYP/ LACVP** calculation level. In the vdW complex of 1… PhCl, chlorobenzene, which interacts weakly with transition metal complex (1), lies above (1)~4.5 Å with a C Cl distance of 1.77 Å. Our calculated structure of the final oxidative addition product, 1_PhCl, shows close resemblance to the experimental X-ray structure, with a RMS deviation of 0.26 Å (heavy-atom only). 5 The calculated Rh C and Rh Cl bond lengths were 2.03 and 2.57 Å, respectively, which are close to the values from the X-ray structures of the Rh pincer complexes. 7 Owing to the steric hindrance exerted by the side chains attached to the P atoms of the POP pincer ligands, the plane of phenyl ring was in the vertical direction with respect to the P-Rh-P bonds. However, in the TS, the plane of phenyl ring is slightly tilted from C Cl axis and rotated by approximately 90 with respect to the plane containing C-Cl-Rh triangle to form Rh C (in phenyl ring) bond. 2 Our computation shows that the lengths of Rh C, Rh Cl, and C Cl bonds are 2.30, 2.60, and 1.93 Å, respectively. This means that Rh, Cl, and C atoms are simultaneously incorporated for concerted singlest...

show abstract

Section: Methodsmentioning

confidence: 99%

normalΔ G = E_{0} + ZPE + normalΔΔ G_{0 \to 298 normalK}

…”

Section: Computational Detailsmentioning

confidence: 99%

Density Functional Theory Study on the Oxidative Addition of Chloroarenes to POP Rhodium Complexes

Kim

Ryu

Hwang

2018

Bulletin Korean Chem Soc

View full text Add to dashboard Cite

show abstract

“…Our attention has been attracted specifically by cross‐coupling reactions of haloarenes catalysed by rhodium complexes . The oxidative addition of haloarenes to rhodium complexes supported by monophosphane, bis(phosphane), pincer and multidentate nitrogen ligands has been studied in depth: the acquired knowledge is important for assessing the reactivity and potential of such rhodium complexes as catalyst precursors for cross‐coupling reactions. Herein, we report on our investigation into the oxidative addition of chloro‐, bromo‐ and iodobenzene to cationic rhodium(I) complexes supported by bis(phosphane) ligands such as DIPAMP (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Oxidative Addition of Aryl Halides to Cationic Bis(phosphane)rhodium Complexes: Application in C–C Bond Formation

et al. 2017

View full text Add to dashboard Cite

show abstract

“…Cross-coupling reactions are traditionally promoted by palladium catalysts, yet cationic diphosphine rhodium complexes have been shown to be also competent catalysts for this important transformation [196]. The oxidative addition of haloarenes to rhodium complexes supported by monophosphine [197][198][199][200], diphosphine [201], pincer [202][203][204][205][206][207][208] and multidentate nitrogen ligands [209,210] has been studied in depth and is assumed to be the first important elementary step in the catalytic cycle of the Suzuki-Miyaura coupling reaction between haloarenes and arylboronic acids. Transmetallation by the nucleophilic partner and subsequent reductive elimination to generate the new C-C bond complete the cycle.…”

Section: Scheme 14mentioning

confidence: 99%

Activation, Deactivation and Reversibility Phenomena in Homogeneous Catalysis: A Showcase based on the Chemistry of Rhodium/Phosphine Catalysts.

et al. 2019

View full text Add to dashboard Cite

In the present work, the rich chemistry of rhodium/phosphine complexes, which are applied as homogeneous catalysts to promote a wide range of chemical transformations, has been used to showcase how the in situ generation of precatalysts, the conversion of precatalysts into the actually active species, as well as the reaction of the catalyst itself with other components in the reaction medium (substrates, solvents, additives) can lead to a number of deactivation phenomena and thus impact the efficiency of a catalytic process. Such phenomena may go unnoticed or may be overlooked, thus preventing the full understanding of the catalytic process which is a prerequisite for its optimization. Based on recent findings both from others and the authors’ laboratory concerning the chemistry of rhodium/diphosphine complexes, some guidelines are provided for the optimal generation of the catalytic active species from a suitable rhodium precursor and the diphosphine of interest; for the choice of the best solvent to prevent aggregation of coordinatively unsaturated metal fragments and sequestration of the active metal through too strong metal–solvent interactions; for preventing catalyst poisoning due to irreversible reaction with the product of the catalytic process or impurities present in the substrate.

show abstract

Selective C–Cl Bond Oxidative Addition of Chloroarenes to a POP–Rhodium Complex

Cited by 36 publications

References 67 publications

Density Functional Theory Study on the Oxidative Addition of Chloroarenes to POP Rhodium Complexes

Density Functional Theory Study on the Oxidative Addition of Chloroarenes to POP Rhodium Complexes

Oxidative Addition of Aryl Halides to Cationic Bis(phosphane)rhodium Complexes: Application in C–C Bond Formation

Activation, Deactivation and Reversibility Phenomena in Homogeneous Catalysis: A Showcase based on the Chemistry of Rhodium/Phosphine Catalysts.

Contact Info

Product

Resources

About