Reactions of TpRu(CO)(NCMe)(Ph) with electron-rich olefins: examples of stoichiometric C–S, C–O and C–H bond cleavage

Goj, Laurel A.; Lail, Marty; Pittard, Karl A.; Riley, Kimberly C.; Gunnoe, T. Brent; Petersen, Jeffrey L.

doi:10.1039/b516407a

Cited by 25 publications

(18 citation statements)

References 28 publications

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“…Ruthenium complexes bearing bis(pyrazolyl)borate (Bp) and tris(pyrazolyl)borate (Tp) ligands have attracted considerable research attentions [24][25][26][27]. However, only a limited number of ruthenium nitrosyl complexes with polypyrazolyborate ligands have been reported [28][29][30][31][32][33][34][35].…”

Section: Introductionmentioning

confidence: 98%

Preparation, characterization, and catalytic properties of ruthenium nitrosyl complexes with polypyrazolylmethane ligands

Cheng

Sun

et al. 2008

Journal of Organometallic Chemistry

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Section: Introductionmentioning

confidence: 98%

Preparation, characterization, and catalytic properties of ruthenium nitrosyl complexes with polypyrazolylmethane ligands

Cheng

Sun

et al. 2008

Journal of Organometallic Chemistry

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“…Reaction Coordinate and Arene Adducts. Scheme 4 shows the proposed reaction sequence for aromatic C-H activation that is based on previous research by our own groups, 12,14,15,57,65 computational studies by Goddard et al, 37 and experimental studies for related TpRh complexes by Jones and co-workers. [66][67][68] The active species for arene activation are the five-coordinate 16-electron systems TpRu(CO)Me and TpRu(PMe 3 )Me.…”

Section: Methodsmentioning

confidence: 99%

Combined Experimental and Computational Studies on the Nature of Aromatic C−H Activation by Octahedral Ruthenium(II) Complexes: Evidence for σ-Bond Metathesis from Hammett Studies

et al. 2007

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Octahedral ruthenium complexes of the type TpRu(L)(NCMe)R [Tp ) hydridotris(pyrazolyl)borate; R ) alkyl or aryl; L ) CO or PMe 3 ] have been shown previously to initiate the C-H activation of aromatic substrates. In order to probe the nature of the C-H activation step, reaction rates have been theoretically obtained for the conversion of TpRu(L)(η 2 -C,C-C 6 H 5 X)Me to TpRu(L)(p-C 6 H 4 X) and CH 4 where X is varied among Br, Cl, CN, F, H, NH 2 , NO 2 , and OMe. A linear Hammett correlation is calculated with a positive F value of 2.6 for L ) CO and 3.2 for L ) PMe 3 . Calculated kinetic data for the aromatic C-H activations indicate that an electrophilic aromatic substitution mechanism is unlikely. While experiments cannot fully replicate the entire range of calculated Hammett plots, reactivity trends are consistent with the calculations that suggest activation barriers to overall metal-mediated arene C-H bond cleavage are reduced by the presence of electron-withdrawing groups in the position para to the site of activation. Previous mechanistic studies, as well as the structure and imaginary vibrational modes of the present transition states, validate that the C-H activation for this family of TpRu complexes occurs through a σ-bond metathesis-type pathway.

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“…[3] In view of the weakness of the electronic interaction between the metal and the C À H bond, [4] which makes functionalization of saturated hydrocarbons a difficult target, research has concentrated on unsaturated hydrocarbons and molecules like alcohols, aldehydes, ethers, amines, and so forth, since metal coordination to a p bond or to a heteroatom can facilitate the selective cleavage of adjoining CÀH bonds. [5] Much of our own work on CÀH bond activation has centered on ethers. Following initial observations of the C À H bond activation of cyclic ethers, [6a] we have recently reported related results on aliphatic ethers [6b] and vinyl ethers.…”

Section: Introductionmentioning

confidence: 99%

Experimental and Computational Studies on the Iridium Activation of Aliphatic and Aromatic CH Bonds of Alkyl Aryl Ethers and Related Molecules

Lara

Paneque

Poveda

et al. 2009

Chemistry A European J

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Reaction of the Ir(III) complex [(Tp(Me2))Ir(C(6)H(5))(2)(N(2))] (1N(2)) with ortho-cresol (2-methylphenol) occurs with cleavage of the O-H and two C(sp(3))-H bonds of the phenol and formation of the electrophilic hydride alkylidene derivative [(Tp(Me2))Ir(H){=C(H)C(6)H(4)-o-O}] (2). The analogous reaction of 2-ethylphenol gives a related product 3. Both 2 and 3 have been shown to be identical to the minor, unidentified products of the already reported reactions of 1 with anisole and phenetole, respectively. Thus, in addition to the route that leads to the known heteroatom-stabilized hydride carbene [(Tp(Me2))Ir(H){=C(H)OC(6)H(4)-o-}] (B), anisole can react with 1 with cleavage of the O-CH(3) bond and formation of a new carbon-carbon bond. In contrast, only C-H bond-activation products with structures akin to B result from 1N(2) and 3,5-dimethylanisole (complex 8) or 4-fluoroanisole (9). Using anisole as a model, a computational study of the triple C-H bond activation (two aliphatic C-H bonds plus an ortho-metalation reaction) that is responsible for the formation of these heteroatom-stabilized hydride carbenes has been undertaken.

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Reactions of TpRu(CO)(NCMe)(Ph) with electron-rich olefins: examples of stoichiometric C–S, C–O and C–H bond cleavage

Abstract: Stoichiometric reactions of TpRu(CO)(NCMe)(Ph) with electron-rich olefins result in metal-mediated cleavage of C-S and C-O bonds.

Cited by 25 publications

References 28 publications

Preparation, characterization, and catalytic properties of ruthenium nitrosyl complexes with polypyrazolylmethane ligands

Preparation, characterization, and catalytic properties of ruthenium nitrosyl complexes with polypyrazolylmethane ligands

Combined Experimental and Computational Studies on the Nature of Aromatic C−H Activation by Octahedral Ruthenium(II) Complexes: Evidence for σ-Bond Metathesis from Hammett Studies

Experimental and Computational Studies on the Iridium Activation of Aliphatic and Aromatic CH Bonds of Alkyl Aryl Ethers and Related Molecules

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