Control of .eta.2-coordination vs. carbon-hydrogen bond activation by rhodium: the role of aromatic resonance energies

Chin, R; Dong, Lichun; Duckett, Simon B.; Partridge, Martin G.; Jones, William D.; Perutz, Robin N.

doi:10.1021/ja00070a012

Cited by 99 publications

(103 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Note that methyl migration to the metal has occurred in this reaction. Perutz and co-workers have reported that a  1 -P−phosphonate rhodium complex 15 was the major product under photochemical conditions in neat arenes of phosphite rhodium complex 14 [63]. Other metalphosphite complexes have been converted to the metal phosphonates by thermolysis [64].…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Anionic phosph(in)ito (“phosphoryl”) ligands: Non-classical “actor” phosphane-type ligands in coordination chemistry

Sutra

Igau

2016

Coordination Chemistry Reviews

View full text Add to dashboard Cite

Section: Methodsmentioning

confidence: 99%

“…Scheme 7. Arbuzov rearrangements in the coordination sphere of rhenium 12 [61] and rhodium 14 [63] metal precursors to form the corresponding  1 -P−phosphonate complexes 13 and 15. [70].…”

Section: Methodsmentioning

confidence: 99%

Anionic phosph(in)ito (“phosphoryl”) ligands: Non-classical “actor” phosphane-type ligands in coordination chemistry

Sutra

Igau

2016

Coordination Chemistry Reviews

View full text Add to dashboard Cite

“…Therefore, the attempt on direct formation of styrene from benzene and ethylene using aromatic C-H bond activation leading to C-C bond formation is a considerably attractive field, which has enough room to be developed from the industrial point of view. As described in Section 1, much work related to homogeneous C-H bond activation of aromatic compounds by discrete transition metal complexes has been reported [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21]. Group VIII metal complexes can also be employed for olefin oxidation reactions such as Pd-catalyzed partial oxidation of ethylene, as is done in the well-known Wacker reaction to form acetaldehyde [61,62] and oxidative vinylation of acetic acid to produce vinyl acetate [63].…”

Section: Conventional Synthesis Of Styrenementioning

confidence: 99%

“…The results of H/D exchange are given in table 11. Complexes [Rh(ppy) 2 Cl] 2 , 3, and 4 are active for deuterium incorporation at 180°C (entries 89-91).…”

Section: Evidence For C-h Activation Of Benzene: H/d Exchange and Addmentioning

confidence: 99%

See 1 more Smart Citation

Transition metal-catalyzed olefin arylation via C–H bond activation of arenes

Matsumoto¹

2007

Catal Surv Asia

View full text Add to dashboard Cite

In this article, two kinds of our transition metal-catalyzed olefin arylations are summarized and discussed. The first one is Ir-catalyzed novel anti-Markovnikov hydroarylation of olefins with benzene. Using this reaction catalyzed by [Ir(l-acac-O,O¢,C 3 )(acac-O,O¢)(acac-C 3 )] 2 (acac = acetylacetonato), 1, straight-chain alkylarenes, which were not obtainable by the conventional Friedel-Crafts aromatic alkylation with olefins, were able to be successfully synthesized directly from arenes and olefins with the higher selectivity than that of branched alkylarenes. This is the first efficient catalyst which shows the desirable high regioselectivity. The reaction of benzene with propylene gave n-propylbenzene and cumene in 61% and 39% selectivities, respectively, and the reaction of benzene and styrene afforded 1,2-diphenylethane in 98% selectivity. The reaction of alkylarene and olefin showed meta and para orientations. A wide range of olefins and arenes can be employed for the synthesis of alkylarenes. The mechanism of the reaction involves C-H bond activation of benzene by Ir center to form Ir-phenyl species. The second reaction is Rh-catalyzed oxidative arylation of ethylene with benzene to directly produce styrene, namely one-step synthesis of styrene. The reaction of benzene with ethylene catalyzed by Rh(ppy) 2 (OAc) (ppyH = 2-phenylpyridine, OAc = acetate), 3 with Cu oxidizing agent gave styrene and vinyl acetate in 77% and 23% selectivities, respectively, in contrast to those by Pd(OAc) 2 , 47% of styrene and 53% of vinyl acetate. The mechanism of the reaction involves Rh-mediated C-H bond activation of benzene, which appears to be a rate-determining step. Furthermore, Rh complexes in a Rh(I) oxidation state at the beginning of the reaction work as catalysts for the reaction by addition of acacH and O 2 without any oxidizing agent, like Cu salt.

show abstract

Stoichiometric Homo-Aldol Coupling of Acetone, Cyclohexanone, and Acetophenone by the [(η5-CpR)Co] (R = Me5, 1,2,4-tri-tert-butyl) Moiety

Schneider¹,

Wolf²,

Bläser³

et al. 2000

Eur. J. Inorg. Chem.

View full text Add to dashboard Cite

Control of .eta.2-coordination vs. carbon-hydrogen bond activation by rhodium: the role of aromatic resonance energies

Cited by 99 publications

References 0 publications

Anionic phosph(in)ito (“phosphoryl”) ligands: Non-classical “actor” phosphane-type ligands in coordination chemistry

Anionic phosph(in)ito (“phosphoryl”) ligands: Non-classical “actor” phosphane-type ligands in coordination chemistry

Transition metal-catalyzed olefin arylation via C–H bond activation of arenes

Stoichiometric Homo-Aldol Coupling of Acetone, Cyclohexanone, and Acetophenone by the [(η5-CpR)Co] (R = Me5, 1,2,4-tri-tert-butyl) Moiety

Contact Info

Product

Resources

About