Intermolecular Oxidative Addition of Aryl Halides to Platinum(II) Alkyl Complexes

2018 ◽  
Author(s):  
Kristof Altus ◽  
Eric Bowes ◽  
D. Dawson Beattie ◽  
Jennifer Love
Keyword(s):  
Aryl Halide ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Aryl Halides ◽  
Alkyl Complexes ◽  
Species Isolation

We report the first well-defined example of intermolecular aryl halide oxidative addition (OA) to Pt(II). Complexes of the type (IMes)PtMe<sub>2</sub>(L) and (IMes’)PtMe(L) (L = SMe<sub>2</sub>, pyridine; IMes = <i>N,N</i>-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; IMes’ = cyclometalated IMes) undergo intermolecular OA of phenyl iodide (PhI) at 60 °C, producing toluene <i>via</i> reductive elimination from a proposed Pt(IV)-phenyl species. Isolation of a model Pt(IV) OA product provides evidence for a Pt(II)/(IV) pathway. The OA of PhI is not limited to Pt(II)-IMes complexes;analogous reactions also proceed with phosphine-ligated Pt(II) dialkyl complexes, demonstrating that this reaction is feasible for a variety of electron-rich Pt(II) complexes bearing labile ligands.

Intermolecular Oxidative Addition of Aryl Halides to Platinum(II) Alkyl Complexes

2018 ◽  
Author(s):  
Kristof Altus ◽  
Eric Bowes ◽  
D. Dawson Beattie ◽  
Jennifer Love
Keyword(s):  
Aryl Halide ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Aryl Halides ◽  
Alkyl Complexes ◽  
Species Isolation

We report the first well-defined example of intermolecular aryl halide oxidative addition (OA) to Pt(II). Complexes of the type (IMes)PtMe<sub>2</sub>(L) and (IMes’)PtMe(L) (L = SMe<sub>2</sub>, pyridine; IMes = <i>N,N</i>-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; IMes’ = cyclometalated IMes) undergo intermolecular OA of phenyl iodide (PhI) at 60 °C, producing toluene <i>via</i> reductive elimination from a proposed Pt(IV)-phenyl species. Isolation of a model Pt(IV) OA product provides evidence for a Pt(II)/(IV) pathway. The OA of PhI is not limited to Pt(II)-IMes complexes;analogous reactions also proceed with phosphine-ligated Pt(II) dialkyl complexes, demonstrating that this reaction is feasible for a variety of electron-rich Pt(II) complexes bearing labile ligands.

Oxidation of Pd(II) with Disilane in a Palladium-Catalyzed Disilylation of Aryl Halides: A Theoretical View

2021 ◽  
Author(s):  
Jing Zhang ◽  
Shihan Liu ◽  
Tao Zhang ◽  
Tao Liu ◽  
Yu Lan
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Dft Calculation ◽  
Aryl Halide ◽  
Oxidative Addition ◽  
Aryl Halides ◽  
Functional Theory ◽  
Theoretical View ◽  
Palladium Catalyzed

Density functional theory (DFT) calculation has been used to reveal the mechanism of Pd-catalyzed disilylation reaction of aryl halide. The DFT calculations indicate that the reaction starts with oxidative addition...

Intermolecular Oxidative Addition of Aryl Halides to Platinum(II) Alkyl Complexes

2019 ◽  
Vol 38 (10) ◽  
pp. 2273-2277 ◽  
Author(s):  
Kristof M. Altus ◽  
Eric G. Bowes ◽  
D. Dawson Beattie ◽  
Jennifer A. Love
Keyword(s):  
Oxidative Addition ◽  
Aryl Halides ◽  
Alkyl Complexes

Reversible Oxidative-Addition and Reductive-Elimination of Thiophene from a Titanium Complex and Its Thermally-Induced Hydrodesulfurization Chemistry

2019 ◽  
Author(s):  
Alejandra Gomez-Torres ◽  
J. Rolando Aguilar-Calderón ◽  
Carlos Saucedo ◽  
Aldo Jordan ◽  
Alejandro J. Metta-Magaña ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Ring Opening ◽  
Thiophene Ring ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Thermally Induced ◽  
Titanium Complex

<p>The masked Ti(II) synthon (<sup>Ket</sup>guan)(<i>η</i><sup>6</sup>-Im<sup>Dipp</sup>N)Ti (<b>1</b>) oxidatively adds across thiophene to give ring-opened (<sup>Ket</sup>guan)(Im<sup>Dipp</sup>N)Ti[<i>κ</i><sup>2</sup>-<i>S</i>(CH)<sub>3</sub><i>C</i>H] (<b>2</b>). Complex <b>2</b> is photosensitive, and upon exposure to light, reductively eliminates thiophene to regenerate <b>1</b> – a rare example of early-metal mediated oxidative-addition/reductive-elimination chemistry. DFT calculations indicate strong titanium π-backdonation to the thiophene π*-orbitals leads to the observed thiophene ring opening across titanium, while a proposed photoinduced LMCT promotes the reverse thiophene elimination from <b>2</b>. Finally, pressurizing solutions of <b>2 </b>with H<sub>2</sub> (150 psi) at 80 °C leads to the hydrodesulfurization of thiophene to give the Ti(IV) sulfide (<sup>Ket</sup>guan)(Im<sup>Dipp</sup>N)Ti(S) (<b>3</b>) and butane. </p>

Carbon-Heteroatom Cross-Coupling via an Electronically Excited Nickel (II) Complex

2019 ◽  
Author(s):  
Randolph Escobar ◽  
Jeffrey Johannes
Keyword(s):  
Energy Transfer ◽  
Functional Groups ◽  
Cross Coupling ◽  
Reductive Elimination ◽  
Aryl Halides ◽  
Coupling Reactions ◽  
General Methodology ◽  
Cross Coupling Reactions ◽  
Electronically Excited ◽  
Energy Transfer Pathway

<div>While carbon-heteroatom cross coupling reactions have been extensively studied, many methods are specific and</div><div>limited to a set of substrates or functional groups. Reported here is a method that allows for C-O, C-N and C-S cross coupling reactions under one general methodology. We propose that an energy transfer pathway, in which an iridium photosensitizer produces an excited nickel (II) complex, is responsible for the key reductive elimination step that couples aryl halides to 1° and 2° alcohols, anilines, thiophenols, carbamates and sulfonamides.</div>

Interconversion of Quadruply and Quintuply Bonded Molybdenum Complexes by Reductive Elimination and Oxidative Addition of Dihydrogen

2013 ◽  
Vol 125 (11) ◽  
pp. 3309-3313 ◽  
Author(s):  
Mario Carrasco ◽  
Natalia Curado ◽  
Celia Maya ◽  
Riccardo Peloso ◽  
Amor Rodríguez ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Reductive Elimination ◽  
Molybdenum Complexes

Reductive elimination of [AlH2]+ from a cationic Ga-Al dihydride

2021 ◽  
Author(s):  
Jun Okuda ◽  
Louis J. Morris ◽  
Laurent Maron ◽  
Ambre Carpentier
Keyword(s):  
Oxidative Addition ◽  
Reductive Elimination ◽  
Metal Bond ◽  
Metal Metal

Oxidative addition of TMEDA-supported [AlH2]+ to [{BDI}Ga] (BDI = {HC(C(CH3)N(2,6-iPr2-C6H3))2) provides [{BDI}Ga(H)-Al(H)(tmeda)]¬[B(C6H3-3,5-Me2)4] (TMEDA = N,N,N’N’-tetramethylethylene¬diamine) with a covalent metal-metal bond. The reaction is readily reversed by substituting TMEDA for an...

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