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Richard J. Puddephatt

Bio: Richard J. Puddephatt is an academic researcher from University of Western Ontario. The author has contributed to research in topics: Oxidative addition & Reductive elimination. The author has an hindex of 11, co-authored 17 publications receiving 879 citations.

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TL;DR: The emission spectra of rigid-rod, conjugated polymeric complexes of gold(I) of the type [−Au−C⋮C−Ar−CµC−C µAuµL−Lµ]x, where Ar = aryl and L−L = diphosphine or bis(isocyanide) ligands are reported for the first time, along with corresponding spectra for analogous mononuclear and binuclear alkynylgold (I) model complexes as discussed by the authors.

187 citations

Journal ArticleDOI
TL;DR: In this article, complete kinetic and thermodynamic parameters have been obtained by VT 1H NMR for the reversible oxidative addition of Me3EX (E = Sn, X = Cl, Br, I) to [PtMe2(bpy-tbu2)] and Me3GeCl to [ptMe 2(bhp-tba2] using the favorability series I > Br > Cl.
Abstract: The reversible oxidative addition reactions of methyl(halogeno)tin and methyl(halogeno)germanium compounds to electron-rich platinum(II) complexes of the type [PtMe2(diimine)] have been studied. Complete kinetic and thermodynamic parameters have been obtained by VT 1H NMR for the reversible oxidative addition of Me3EX (E = Sn, X = Cl, Br, I) to [PtMe2(bpy-tbu2)] (bpy-tbu2 = 4,4‘-di-tert-butyl-2,2‘-bipyridyl) and related compounds, while partial data have been obtained for the reductive elimination of Me2SnCl2 from [PtClMe2(Me2SnCl)(bpy-tbu2)] and for the oxidative addition of Me3GeCl to [PtMe2(bpy-tbu2)]. UV−visible spectroscopic studies have also yielded equilibrium constants and ΔG° for the reversible oxidative addition reactions of Me3SnX (X = Cl, Br, I) to [PtMe2(diimine)]. Thermodynamic studies quantitatively establish the halogen effect on the oxidative addition reactions studied according to the favorability series I > Br > Cl. Kinetic studies clearly point to an SN2 mechanism for the reactions stu...

70 citations

Journal ArticleDOI
TL;DR: The degree of stereoselectivity in intramolecular oxidative addition of aryl−halogen bonds to platinum(II) has been determined using the following diimine ligands based on trans- or cis-1,2-diamino as discussed by the authors.

35 citations


Cited by
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TL;DR: This review discusses the synthetic methodologies that are currently available for the preparation of platinum group metal complexes containing pincer ligands and especially emphasizes different applications that have been realized in materials science such as the development and engineering of sensors, switches, and catalysts.
Abstract: Since the first reports in the late 1970s on transition metal complexes contain- ing pincer-type ligands—named after the particular coordination mode of these ligands—these systems have at- tracted increasing interest owing to the unusual properties of the metal centers imparted by the pincer ligand. Typical- ly, such a ligand comprises an anionic aryl ring which is ortho,ortho-disubsti- tuted with heteroatom substituents, for example, CH2NR2 ,C H 2PR2 or CH2SR, which generally coordinate to the met- al center, and therefore support the MC s bond. This commonly results in a terdentate and meridional coordina- tion mode consisting of two metalla- cycles which share the MC bond. Detailed studies of the formation and the properties of a large variety of pincers containing platinum group metal complexes have provided direct access to both a fundamental under- standing of a variety of reactions in organometallic chemistry and to a range of new applications of these complexes. The discovery of alkane dehydrogenation catalysts, the mecha- nistic elucidation of fundamental transformations (for example, CC bond activation), the construction of the first metallodendrimers for sustain- able homogeneous catalysis, and the engineering of crystalline switches for materials processing represent only a few of the many highlights which have emanated from these numerous inves- tigations. This review discusses the synthetic methodologies that are cur- rently available for the preparation of platinum group metal complexes con- taining pincer ligands and especially emphasizes different applications that have been realized in materials science such as the development and engineer- ing of sensors, switches, and catalysts.

1,413 citations

Journal ArticleDOI
TL;DR: The Shilov-type Chemistry, “Catalytica” System for Catalytic Methane Functionalization, and Computational Studies of theShilov System are presented.
Abstract: 2.3. Hydrocarbon Coordination 2475 2.4. σ Complexes of Alkanes and Arenes 2475 2.5. Principle of Microscopic Reversibility 2476 2.6. Kinetic Isotope Effects 2477 3. Shilov-type Chemistry 2478 3.1. C−H Activation by Pt(II) 2479 3.2. Mechanism of Multiple H/D Exchange 2480 3.3. H/D Exchanges1,2 Shift in Ethane 2481 3.4. Computational Studies of the Shilov System 2481 3.5. C−H Activation by Pt(IV) 2482 4. “Catalytica” System for Catalytic Methane Functionalization 2482

689 citations