Activation of the carbon-hydrogen bonds of benzene by reaction with [bis(dicyclohexylphosphino)ethane]platinum(0), generated by the thermolysis of cis-[bis(dicyclohexylphosphino)ethane]hydridoneopentylplatinum(II)

Hackett, Marifaith.; Ibers, James A.; Whitesides, George M.

doi:10.1021/ja00213a015

Cited by 118 publications

(67 citation statements)

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“…[102] The characterization of the products was often achieved by in situ NMR spectroscopy of the reaction solution. [128,129] with R 3 E (R CH 2 tBu, CH 2 SiMe 3 ; E Al, Ga, In; L (C 6 H 11 )PCH 2 CH 2 P(C 6 H 11 )) as reaction partner and at the same time as solvent [Eq. (7)].…”

Section: Bimolecular Addition Reactions Of Alkyl Earth Metal Compoundmentioning

confidence: 99%

“…The reactive fragment thus formed, [cis-(L) 2 Pt], then is available for a series of subsequent reactions. [128,129] It has to be emphasized that the course of the reaction is strongly influenced by small variations of the groups R. According to Equation (8) quantitative alkylation or alkyl exchange and the formation of [(L) 2 PtR 2 ] is observed for R CH 3 , C 2 H 5 , isobutyl. The work of Schneider et al on the interaction of alkylaluminum compounds with transition metal fragments should be noted in this context.…”

Section: Bimolecular Addition Reactions Of Alkyl Earth Metal Compoundmentioning

confidence: 99%

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Coordination Chemistry of Aluminum, Gallium, and Indium at Transition Metals

Fischer

Weiß

1999

Angew. Chem. Int. Ed.

208

101

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The current upswing in the interest in organoelement chemistry of Group 13 metals is attributed not least to the establishment of the coordination chemistry of R(a)E fragments (E=Al, Ga, In; a=1, 2) at d-block metals (M). Recently the availability of low-valent organoelement compounds as building blocks for synthesis has substantially enriched the structure chemistry of this class of compounds. The M-E bonding conditions and the question of the significance of M(d(pi))-E(p(pi)) backbonding as well as potential applications in materials science, for example, as single-source precursors for the deposition of thin intermetallic films by chemical vapor deposition, are discussed.

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Section: Bimolecular Addition Reactions Of Alkyl Earth Metal Compoundmentioning

confidence: 99%

Section: Bimolecular Addition Reactions Of Alkyl Earth Metal Compoundmentioning

confidence: 99%

Coordination Chemistry of Aluminum, Gallium, and Indium at Transition Metals

Fischer

Weiß

1999

Angew. Chem. Int. Ed.

208

101

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“…These studies [30][31][32][33][34] , along with parallel, beautiful, studies by Bergman [35] , played a useful role in establishing the facility with which late transition metals could cleave (either intra-or intermolecularly) unactivated aliphatic C-H bonds. These studies were extensive, but involved conceptually straightforward examinations of products: the characterization of C-H bonds by examining the shuffling of deuterium in isotopically labeled species using NMR or mass spectroscopy [30] .…”

Section: Intramolecular Reactions In Organoplatinum(ii) Compoundsmentioning

confidence: 97%

Physical‐Organic Chemistry: A Swiss Army Knife

Whitesides

2015

Israel Journal of Chemistry

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Abstract"Physical-organic chemistry" is the name given to a subfield of chemistry that applies physical-chemical techniques to problems in organic chemistry (especially problems involving reaction mechanisms). "Physical-organic" is, however, also a short-hand term that describes a strategy for exploratory experimental research in a wide range of fields (organic, organometallic, and biological chemistry; surface and materials science; catalysis; and others) in which the key element is the correlation of systematic changes in molecular structure with changes in properties and functions of interest (reactivity, mechanism, physical or biological characteristics). This perspective gives a personal view of the historical development, and of possible future applications, of the physical-organic strategy.

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“…The first involves the oxidative addition of the C-H bond to an unsaturated metal fragment, and is typical of electron-rich late metal systems [5][6][7][8][9][10][11][12][13]. The second takes place by a 1,2-R-H addition, in which the C-H bond adds across a highly electrophilic d o metal M-X bond [14][15][16][17][18][19][20][21][22][23][24].…”

Section: Abstract: Iridium; C-h Activation; Metallacyclesmentioning

confidence: 99%

CH bond activation in functionalized organic compounds with Cp∗ (PMe3)IrMe(OTf): generation, structural characterization and metal-based rearrangement of the acetone activation product Cp∗ (PMe3)Ir(η3-CH2C(OH)CH2)+OTf−

Arndtsen

Bergman

1995

Journal of Organometallic Chemistry

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The iridium complex Cp'(PMe3)Ir(Me)OTf (1) (Cp*= rlS-Cs(CH3)5, OTf=OSO2CF 3) reacts cleanly with acetone at room temperature. This reaction results in overall double C-H activation, generating the cationic rl3-hydroxyallyl complex Cp * (PMe3)Ir(r/3-CH2C(OH)CH2)+OTf -(2). Complex 2 was characterized by X-ray diffraction and found to contain a hydrogen-bonded triflate anion. The ultimate product formed on reaction with acetone is strongly dependent upon the nature of the counterion present. Replacement of the triflate ion in 2 with other anions leads to the metallacyclobutanone Cp'(PMe3)Ir(rl2-CH2COCH2), the rll-enolate Cp*(PMe3)lr(CH2COCH3)S(p-tolyl) and the free cation salt Cp'(PMe3)Ir(r/3-CH2C(OH)CH2) + B(3,5-C6H3(CF3)2)~-. Keywords: Iridium; C-H activation; MetallacyclesCarbon-hydrogen (C-H) bond activation research during the past decade has demonstrated two general processes by which certain transition metal complexes can effect the stoichiometric cleavage of carbon-hydrogen bonds [1][2][3][4]. The first involves the oxidative addition of the C-H bond to an unsaturated metal fragment, and is typical of electron-rich late metal systems [5][6][7][8][9][10][11][12][13]. The second takes place by a 1,2-R-H addition, in which the C-H bond adds across a highly electrophilic d o metal M-X bond [14][15][16][17][18][19][20][21][22][23][24]. This dichotomy has led to significant limitations in the scope and chemistry of transition-metal based C-H bond activation. The late metal complexes are often highly reactive, thereby generating complicated mixtures when different types of C-H bond are present in a reacting molecule. Also, the coordinatively saturated products are generally resistant to subsequent reactions and/or rearrangements designed to transform the C-H activated complex into a functionalized organic compound [25][26][27] while the or-bond metathesis systems do generally demonstrate significant bond selectivities (e.g. primary >> secondary, tertiary) and contain an empty coordination site, the oxophilic metals that typify these complexes are often not compatible with common organic functional groups.We recently reported that the iridium complex Cp*(PMe3)IrMe(OTf) (1) (Cp* = r/5-Cs(CH3)5, OTf = OSO2CF 3) reacts at ambient temperature with alkanes and arenes R-H to generate methane and the corresponding Ir-R complexes [28]. In contrast to typical bond activations with electron-rich metal fragments, these reactions are relatively mild, requiring neither photolysis nor elevated temperature, and are highly selective for methane primary and/or arene C-H bonds. In addition, the electron-rich metal center appears to be compatible with heteroatom-containing functional groups, allowing the use of methylene chloride as a solvent for these reactions. In an effort to extend the generality of this unusual and selective o-bond metathesis-like chemistry, we have begun to explore the activation of C-H bonds in organic substrates containing functional groups. Herein we report the clean reaction

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Activation of the carbon-hydrogen bonds of benzene by reaction with [bis(dicyclohexylphosphino)ethane]platinum(0), generated by the thermolysis of cis-[bis(dicyclohexylphosphino)ethane]hydridoneopentylplatinum(II)

Cited by 118 publications

References 1 publication

Coordination Chemistry of Aluminum, Gallium, and Indium at Transition Metals

Coordination Chemistry of Aluminum, Gallium, and Indium at Transition Metals

Physical‐Organic Chemistry: A Swiss Army Knife

CH bond activation in functionalized organic compounds with Cp∗ (PMe3)IrMe(OTf): generation, structural characterization and metal-based rearrangement of the acetone activation product Cp∗ (PMe3)Ir(η3-CH2C(OH)CH2)+OTf−

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