Study of the Mechanism of Photochemical Carbonylation of Benzene Catalyzed by Rh(PMe3)2(CO)Cl

Rosini, Glen P.; Boese, William T.; Goldman, Alan S.

doi:10.1021/ja00100a013

Cited by 68 publications

(43 citation statements)

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“…Elegant studies carried out by Goldman have established that, contrary to expectation, C-H activation occurs between substrate and an excited state of the intact catalyst [74]. The resulting octahedral species undergoes secondary photolysis to yield products, Fig.…”

Section: Oxidative Addition Without Co-lossmentioning

confidence: 91%

Organometallic photochemistry at the end of its first century

Bitterwolf

2004

Journal of Organometallic Chemistry

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Section: Oxidative Addition Without Co-lossmentioning

confidence: 91%

Organometallic photochemistry at the end of its first century

Bitterwolf

2004

Journal of Organometallic Chemistry

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“…The short-wavelength mechanism was proposed to proceed via direct C-H oxidative addition to an intact, four coordinate, photoexcited species; a second photon was then required to induce alkyl-to-CO migration. Based on these findings, it was possible to select conditions that resulted in greatly increased turnover numbers, quantum yields and selectivity via the short-wavelength mechanism (100,104). The duality of mechanisms received strong support from TRIR studies by Ford (95) and Bitterwolf (99).…”

Section: Insertion Of Co and Isonitriles Into C-h Bondsmentioning

confidence: 98%

“…In a somewhat puzzling twist, it was found that with short-wavelength light, «-alkanes could be carbonylated with regioselectivity for the terminal position, but longer wavelengths gave primarily branched aldehydes (102). This reaction was proposed by Field and Goldman to proceed via two distinct mechanisms (100,103,104). The long-wavelength mechanism effected C-H activation via photoelimination of CO, followed by C-H addition.…”

Section: Insertion Of Co and Isonitriles Into C-h Bondsmentioning

confidence: 99%

Organometallic C—H Bond Activation: An Introduction

Goldman¹,

Goldberg²

2004

ACS Symposium Series

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117

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An introduction to the field of activation and fimctionalization of C-H bonds by solution-phase transition -metal-based systems is presented, with an emphasis on the activation of aliphatic C-H bonds. The focus of this chapter is on stoichiometric and catalytic reactions that operate via organometallic mechanisms, i.e., those in which a bond is formed between the metal center and the carbon undergoing reactionThe carbon-hydrogen bond is the un-functional group. Its unique position in organic chemistry is well illustrated by the standard representation of organic molecules: the presence of C-H bonds is indicated simply by the absence of any other bond. This "invisibility" of C-H bonds reflects both their ubiquitous nature and their lack of reactivity. With these characteristics in mind it is clear that if the ability to selectively fiinctionalize C-H bonds were well developed, it could potentially constitute the most broadly applicable and powerful class of transformations in organic synthesis. Realization of such potential could revolutionize the synthesis of organic molecules ranging in complexity from methanol to the most elaborate natural or unnatural products.The following chapters in this volume offer a view of many of the current leading research efforts in this field, in particular those focused on the activation

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“…Catalytic dehydrogenation of hexane, heplengths shorter than 320 nm by Goldman et al [22] Under tane, and octane has been carried out by Saito [16] using these conditions, the authors propose that the first step is RhCl(CO)(PR 3 ) 2 (R ϭ Me, Et, Ph), and Tanaka [17] using the oxidative addition of a benzene CϪH bond to a photo-RhCl(CO)(PMe 3 ) 2 . Catalytic dehydrogenation of hexane, heplengths shorter than 320 nm by Goldman et al [22] Under tane, and octane has been carried out by Saito [16] using these conditions, the authors propose that the first step is RhCl(CO)(PR 3 ) 2 (R ϭ Me, Et, Ph), and Tanaka [17] using the oxidative addition of a benzene CϪH bond to a photo-RhCl(CO)(PMe 3 ) 2 .…”

Section: Alkane Dehydrogenationmentioning

confidence: 99%

Catalytic Formation of Carbon–Carbon Bonds by Activation of Carbon–Hydrogen Bonds

Guari

Sabo-Étienne

Chaudret³

1999

Eur. J. Inorg. Chem.

219

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The direct functionalization of C–H bonds by formation of a C–C bond is an interesting and important alternative to coupling reactions involving halide derivatives. These reactions are complex but during the past few years a number of new systems have been developed which display promising scope. This microreview will briefly mention the different mechanisms leading to C–H activation and describe the new systems leading to the catalytic formation of carbon–carbon bonds.

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Study of the Mechanism of Photochemical Carbonylation of Benzene Catalyzed by Rh(PMe3)2(CO)Cl

Cited by 68 publications

References 0 publications

Organometallic photochemistry at the end of its first century

Organometallic photochemistry at the end of its first century

Organometallic C—H Bond Activation: An Introduction

Catalytic Formation of Carbon–Carbon Bonds by Activation of Carbon–Hydrogen Bonds

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