Platinum-Catalyzed Phenyl and Methyl Group Transfer from Tin to Iridium:  Evidence for an Autocatalytic Reaction Pathway with an Unusual Preference for Methyl Transfer

Smith, Stuart E.; Sasaki, Jennifer M.; Bergman, Robert G.; Mondloch, Joseph E.; Finke, Richard G.

doi:10.1021/ja710365x

Cited by 35 publications

(69 citation statements)

References 19 publications

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“…This led to identification of the previously hidden PtCl( t -Bu 3 P) 2 (SnMe 3 ) catalyst, after which it proved easy to write the catalytic cycle. 16 This example is the presently best available example we are aware of illustrating the power of the minimalistic, simple 2-step mechanism to reveal an underlying catalyst and more complex mechanism that, prior to the fit to the 2-step mechanism, was completely obscure and at an intractable standstill prior to the fit to the 2-step mechanism. 16…”

Section: Resultsmentioning

confidence: 95%

“…(i) The first of these is our collaboration with the Bergman research group, where the development of a homogeneous catalyst showed sigmoidal, autocatalytic kinetics but where the true catalyst and the underlying catalytic mechanism remained completely obscure. 16 To get at the mechanism, a fit to the 2-step mechanism was done and yielded a good fit. That good fit, in turn, revealed that figuring out what “ B ” is was key, B being the true, but hidden, catalyst in the reaction.…”

Section: Resultsmentioning

confidence: 99%

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Gold Nanoparticle Formation Kinetics and Mechanism: A Critical Analysis of the “Redox Crystallization” Mechanism

Watzky

Finke

2018

ACS Omega

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A 2013 paper proposed a “redox crystallization” (R-C) mechanism for the formation of Au 0 n nanoparticles from the reduction of a AuCl 4 – precursor. That study used an unconventional analysis of the valuable, expertly obtained kinetics data reported, and came up with multiple claims and insights collected under the putatively new R-C mechanism. If confirmed, those claims and the R-C mechanism provide a valuable addition to the knowledge of gold nanoparticle formation kinetics and mechanisms. On the other hand, if the methodology used to support the R-C mechanism is flawed so that its resultant conclusions are incorrect, then the R-C mechanism needs to be discarded until compelling evidence for it can be gathered, evidence that would have to include the disproof of the other dominant mechanism(s) of nanoparticle formation. The present work provides a critical analysis of the evidence previously offered for the R-C mechanism, efforts that are of interest to the areas of Au 0 n nanoparticles, the kinetics and mechanisms of nanoparticle formation and, as it turns out, more generally to those interested in kinetic and mechanistic studies.

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Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 99%

Gold Nanoparticle Formation Kinetics and Mechanism: A Critical Analysis of the “Redox Crystallization” Mechanism

Watzky

Finke

2018

ACS Omega

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“…In another example, a heterometallic Pt(CH3)-Sn(CH3)3 species has been proposed as a key intermediate in the platinum catalyzed methyl transfer from methyl tin reagents to iridium complexes. 246 Transmetalation reactions are also employed as a convenient strategy to access mono-methyl species alike LnM(CH3)X through metathesis of LnM(CH3)2 and LnM(X)2. The opposite, disproportionation of mono-methyl compounds to afford dimethyl metal derivatives has been recently investigated over Pd(II) species.…”

Section: Reactivity Of Transition Metal M(μ-ch3)m Bridging Compoundsmentioning

confidence: 99%

“…The dissimilar behavior of ZnMe 2 with respect to ZnMeCl has also been analyzed. In another example, a heterometallic Pt(CH 3 )–Sn(CH 3 ) 3 species has been proposed as a key intermediate in the platinum catalyzed methyl transfer from methyl tin reagents to iridium complexes . Transmetalation reactions are also employed as a convenient strategy to access monomethyl species like [L n M(CH 3 )X] through metathesis of [L n M(CH 3 ) 2 ] and [L n M(X) 2 ].…”

Section: Reactivitymentioning

confidence: 99%

Methyl Complexes of the Transition Metals

Campos

López‐Serrano

Peloso

et al. 2016

Chemistry A European J

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Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, i.e. based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition metal complexes containing M-CH3 fragments. Taking into account the impressive amount of data that are continuously provided by organometallic chemists in this area, this review is mainly focused on results of the last 5 years. After a panoramic overview on M-CH3 compounds of groups 3 to 11 which includes the most recent landmark findings in this area, two further sections are dedicated to methyl-bridged complexes and reactivity.

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“…Bergman and co-workers have reported a beautiful example of Pt-catalyzed Ph and Me group transfer from Sn to Ir, in which an autocatalytic reaction was observed, in addition to preference for Me transfer, which is opposite to the usual aryl preference of transmetalation from tin. [44] The autocatalytic reaction starts when the formation of SnMe 3 Cl as byproduct of the slow direct methylation of the Ir complex allows for the formation of the Pt…”

Section: Introductionmentioning

confidence: 99%

Bimetallic Catalysis using Transition and Group 11 Metals: An Emerging Tool for CC Coupling and Other Reactions

Pérez‐Temprano

Casares

Espinet

2012

Chemistry A European J

214

131

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Bimetallic catalysis refers to homogeneous processes in which either two transition metals (TM), or one TM and one Group 11 (G11) element (occasionally Hg also), cooperate in a synthetic process (often a C-C coupling) and their actions are connected by a transmetalation step. This is an emerging research area that differs from the isolated or tandem applications of the now classic processes (Stille, Negishi, Suzuki, Hiyama, Heck). Most of the reactions used so far combine Pd with a second metal, often Cu or Au, but syntheses involving very different TM couples (e.g., Cr/Ni in the catalyzed vinylation of aldehydes) have also been developed. Further development of the topic will soon demand a good knowledge of the mechanisms involved in bimetallic catalysis, but this knowledge is very limited for catalytic processes. However, there is much information available, dispersed in the literature, coming from basic research on exchange reactions occurring out of any catalytic cycle, in polynuclear complexes. These are essentially the same processes expected to operate in the heart of the catalytic process. This Review gathers together these two usually isolated topics in order to stimulate synergy between the bimetallic research coming from more basic organometallic studies and the more synthetic organic approaches to this chemistry.

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Platinum-Catalyzed Phenyl and Methyl Group Transfer from Tin to Iridium: Evidence for an Autocatalytic Reaction Pathway with an Unusual Preference for Methyl Transfer

Cited by 35 publications

References 19 publications

Gold Nanoparticle Formation Kinetics and Mechanism: A Critical Analysis of the “Redox Crystallization” Mechanism

Gold Nanoparticle Formation Kinetics and Mechanism: A Critical Analysis of the “Redox Crystallization” Mechanism

Methyl Complexes of the Transition Metals

Bimetallic Catalysis using Transition and Group 11 Metals: An Emerging Tool for CC Coupling and Other Reactions

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