Synthesis and thermolysis of dimethylbis(trialkylphosphine)platinum(II) complexes in which the phosphine ligands contain adamantyl, adamantylmethyl, and methyl groups

Hackett, Marifaith.; Whitesides, George M.

doi:10.1021/om00145a027

Cited by 19 publications

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“…Ligands coordinate the Pt atom in such geometrical arrangement that intramolecular carbometalation of the C-H bond at C2 of the adamantane framework takes place at 215 °C with complex 74 being formed and simultaneously releasing a molecule of methane (Scheme 29). 46 The mechanism of the carbometalation step was not proposed. The authors made the following note, 'cyclometalation occurs most readily when the ligand is bulky and a five-membered metallacycle results, four-and six-membered metallacycles are formed somewhat less readily, and three-membered metallacycles are usually formed only when no other options for cyclometalation are available'.…”

Section: Short Review Syn Thesismentioning

confidence: 99%

Directed C–H Functionalization of the Adamantane Framework

Hrdina¹

2018

Synthesis

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This review summarizes the synthetic approaches towards 1,2-substitution pattern on the adamantane framework. Selected are the works containing the directed C–H functionalization step.1 Introduction2 Access to 1,2-Disubstituted Derivatives via C–H Insertion Reactions of Electrophilic Organic Species3 Access to 1,2-Disubstituted Derivatives through Hydrogen Radical Abstraction Reactions4 Access to 1,2-Disubstituted Derivatives Exploiting Metal-Catalyzed (Promoted) C–H Activations5 Access to 1,2-Disubstituted Derivatives via Hydride Shift6 Conclusion7 Acronyms

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Section: Short Review Syn Thesismentioning

confidence: 99%

Directed C–H Functionalization of the Adamantane Framework

Hrdina¹

2018

Synthesis

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“…The 1-adamantyl group can be installed by a classic route for tertiary phosphine synthesis involving an S N 2type reaction of 1-AdMgBr with a halophosphine (Scheme 2, a). 2j However, reactions of 1-AdMgBr with ClPAd 2 failed to generate appreciable amounts of PAd 3 in the presence, or absence, 17 of a copper catalyst (Scheme 2, b). On the other…”

Section: Synthesis Of Tri(1-adamantyl)phosphinementioning

confidence: 99%

Tri(1-adamantyl)phosphine: Exceptional Catalytic Effects Enabled by the Synergy of Chemical Stability, Donicity, and Polarizability

Carrow

Chen

2017

Synlett

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Tri(1-adamantyl)phosphine, a simple yet long-absent homoleptic phosphine, has finally been prepared. The simplicity of this compound beguiles its exceptional properties. The electron-releasing character eclipses all other alkylphosphines. The phosphine geometry and overall size are also more compact than anticipated, which may occur as a result of dispersion forces. We believe the donicity, marked resistance towards cyclometallation or P−C bond scission, and also substantial polarizability engendered by the three diamondoid fragments together account for the phenomenal performance of Pd-PAd 3 catalysts during Suzuki-Miyaura coupling reactions. A correlation analysis is also described that provides support for polarizability as a potentially general influence on the properties of tertiary phosphines. 1 Introduction 2 Synthesis of Tri(1-adamantyl)phosphine 3 Reactions of Tri(1-adamantyl)phosphine Palladium Complexes 4 Electronic and Steric Properties of Tri(1-adamantyl)phosphine 5 Conclusion Key words phosphine, ligand, catalysis, cross-coupling, palladium, diamondoid Liye Chen (right) is originally from Dalian, China. In 2008, he obtained a BS in chemistry from Tsinghua University in Beijing, China and then completed post-undergraduate research at the Shanghai Institute of Organic Chemistry. Currently, Liye is a Ph.D. candidate at Princeton in Brad Carrow's laboratory and is pursuing catalyst and reaction discovery and development. Brad Carrow (left) obtained his B.S. in chemistry from the Missouri University of Science and Technology in 2003. He received his in Ph.D. in 2011 from the University of Illinois at Urbana-Champaign following work in the laboratories of John F. Hartwig. After completing his graduate studies, he was a postdoctoral fellow and then an assistant professor in the laboratories of Kyoko Nozaki at the University of Tokyo. Since Fall 2013, he has been an assistant professor of chemistry at Princeton University. His research interests revolve around transition-metal catalysis in the context of sustainable organic synthesis, polymer synthesis, and strong bond activation.

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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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Synthesis and thermolysis of dimethylbis(trialkylphosphine)platinum(II) complexes in which the phosphine ligands contain adamantyl, adamantylmethyl, and methyl groups

Cited by 19 publications

References 0 publications

Directed C–H Functionalization of the Adamantane Framework

Directed C–H Functionalization of the Adamantane Framework

Tri(1-adamantyl)phosphine: Exceptional Catalytic Effects Enabled by the Synergy of Chemical Stability, Donicity, and Polarizability

Physical‐Organic Chemistry: A Swiss Army Knife

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