scholarly journals Oxidative additions of alkynyl/vinyl iodides to gold and gold-catalyzed vinylation reactions triggered by the MeDalphos Ligand

2021 ◽  
Author(s):  
Jessica Rodriguez ◽  
Alexis Tabey ◽  
Sonia Ladeira ◽  
Didier Bourissou
Keyword(s):  
Oxidative Addition ◽  
Oxidative Additions ◽  
Vinyl Iodides

The hemilabile Ad2P(o-C6H4)NMe2 ligand promotes fast, quantitative and irreversible oxidative addition of alkynyl and vinyl iodides to gold. The reaction is general. It works with a broad range of substrates...

Dinuclear oxidative addition reactions using an isostructural series of Ni2, Co2, and Fe2 complexes

2017 ◽  
Vol 46 (17) ◽  
pp. 5493-5497 ◽  
Author(s):  
Michael J. Behlen ◽  
You-Yun Zhou ◽  
Talia J. Steiman ◽  
Sudipta Pal ◽  
Douglas R. Hartline ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Addition Reactions ◽  
Oxidative Additions ◽  
Redox Active ◽  
Metal Metal ◽  
Metal Metal Bonds ◽  
Metal Bonds

Dinuclear oxidative additions at metal–metal bonds are facilitated by redox-active supporting ligands.

Insight into the reaction mechanisms for oxidative addition of strong σ bonds to an Al(i) center

2016 ◽  
Vol 45 (25) ◽  
pp. 10355-10365 ◽  
Author(s):  
Xiangfei Zhang ◽  
Zexing Cao
Keyword(s):  
Reaction Mechanisms ◽  
Oxidative Addition ◽  
Oxidative Additions ◽  
Insight Into

The oxidative additions of σ X–H bonds to an Al(i) center follow different mechanisms depending on their bonding features and local structural environments.

Oxidative Addition von Tetramethyldiphosphan und -arsan an Cp′–SiMe2–Cp′-überbrückte Molybdän- und Wolframcarbonyl-Komplexe / Oxidative Addition of Tetramethyldiphosphane and -arsane to Binuclear Cp′–SiMe2–Cp′-Bridged Molybdenum and Tungsten Carbonyl Complexes

1991 ◽  
Vol 46 (7) ◽  
pp. 841-852 ◽  
Author(s):  
Walter Abriel ◽  
Gerhard Baum ◽  
Heike Burdorf ◽  
Jürgen Heck
Keyword(s):  
Oxidative Coupling ◽  
Oxidative Addition ◽  
Thermal Reaction ◽  
Carbonyl Complexes ◽  
Metal Centers ◽  
X Ray ◽  
Nmr Data ◽  
Oxidative Additions ◽  
Tungsten Carbonyl

Thermal reaction of Me2Si[Cp′M(CO)3]2 (M = Mo, W; Cp′ = C5H4) with tetramethyldiphosphane and -diarsane gives oxidative coupling products with bridging EMe2-groups (E = P, As). With E = P discrete binuclear compounds are obtained, which on further thermolysis afford new species of the general formula {Me2Si(Cp′M)2(CO)3(μ-PMe2)2} (5). X-Ray structure determination of 5 a (M = Mo) and NMR data show a PMP-heteroallylic system which is bound to the second metal. In the case of M = W a second compound with a mixed hydrido and dimethylphosphido bridge can be isolated, which shows fluxionality in solution. However, the oxidative additions with tetramethyldiarsane lead to insoluble products which are assumed to be polymeric with Cp′–SiMe2–Cp′ as well as AsMe2 bridges linking the metal centers.

Chemie polyfunktioneller Liganden, 57 [1] Über Iridium(I)- und Platin(II)-Komplexe des Bis(diphenylphosphino)amins und die oxidative Addition kleiner Moleküle an Di[bis(diphenylphosphino)amin-P.P']iricUum(I)-chlorid / Chemistry of Polyfunctional Ligands, 57[1] About Iridium(I) and Platinum(II) Complexes of Bis(diphenylphosphino)amine and the Oxidative Addition of Small Molecules to Di[bis(diphenylphosphino)amine]iridium(I)-chloride

1980 ◽  
Vol 35 (3) ◽  
pp. 307-315 ◽  
Author(s):  
Jochen Ellermann ◽  
Leo Mader
Keyword(s):  
Small Molecules ◽  
Nmr Spectra ◽  
Oxidative Addition ◽  
Molar Ratio ◽  
Ionic Complex ◽  
Oxidative Additions ◽  
Square Planar ◽  
Deuterated Derivative ◽  
New Compounds

R2PNHPR2 (1) (R = C6H5) reacts with [(μ-Cl)Ir(C8H12)]2 in a molar ratio of 4:1, to give the square planar, ionic complex [Ir(R2PNHPR2)2]Cl (2a). By reaction of 2a with NaBR4, [Ir(R2PNHPR2)2]BR4 (2b) is obtained. Treatment of 2 a with CO gives [Ir(CO)(R2PNHPR2)2]Cl (3a). The complex 3a is also formed by the reaction of 1 with Ir(CO)(PR3)2Cl (R = C6H5) and Ir(CO)2(p-H2N-C6H4-CH3)Cl. 3a undergoes metathesis with NH4PF6 to yield [Ir(CO)(R2PNHPR2)2]PF6 (3b). The N-deuterated derivative [Ir(CO)(R2PNDPR2)2]Cl (4) is made by H/D exchange from 3a with CH3OD. Oxidative additions of O2 , CS2, I2 and (SCN)2 to 2a yield [Ir(O2)(R2PNHPR2)2]Cl (5), [Ir(μ2-CS2)(R2PNHPR2)2]Cl (6), [Ir(I)2(R2PNHPR2)2]Cl (7) and [Ir(SCN)2(R2PNHPR2)2]Cl (8). Additionally K2[PtCl4] and 1 reacts to [Pt(R2PNHPR2)2]Cl2 (9). The new compounds are characterised, as far as possible, by their IR, FIR, Raman and 31P NMR spectra.

OXIDATIVE ADDITION OF C–X BOND IN HCCX (X = H, CH3, ANDSiH3) TO RHODIUM(I) COMPLEX AND SUBSEQUENT 1,3-MIGRATION OF X: A DFT LEVEL STUDY

2005 ◽  
Vol 04 (01) ◽  
pp. 59-73 ◽  
Author(s):  
CHERUMUTTATHU H. SURESH ◽  
NOBUAKI KOGA
Keyword(s):  
Density Functional ◽  
Oxidative Addition ◽  
Functional Theory ◽  
Ethynyl Group ◽  
Density Functional Theory Level ◽  
Energy Profiles ◽  
Oxidative Additions ◽  
The Density Functional Theory ◽  
Silyl Groups ◽  
One Step

Oxidative addition of the C – X bond in HCCX ( X = H , CH 3, SiH 3) to RhCl ( PH 3)2, as well as the subsequent 1,3-migration of the substituent X from Rh to the β carbon of the ethynyl group leading to vinylidine-Rh complex, is studied using the localized molecular orbital (LMO) analysis at the density functional theory level. The highest Δ G ‡ values of 20.2, 16.3, and 18.5 kcal/mol are obtained respectively for the endothermic C–H bond oxidative additions of HCCH , HCCCH 3, and HCCSiH 3, which correspond to the slippage of the η2 alkyne complex RhCl (η2- HCCX )( PH 3)2. The 1,3-hydrogen migration, a one step process from Rh(H)(CCX)(Cl) ( PH 3)2 proceeds via a three center transition state involving H ⋯( CC ) interactions with Δ G ‡ values of 18.7, 16.3, and 18.1 kcal/mol for X = H , CH 3, and SiH 3, respectively. The overall nature of the reaction profiles and the LMO features suggest nearly identical behavior for all the C – H bond oxidative additions as well as the 1,3-hydrogen migrations. However, the energy profiles and LMO features of the C – CH 3 and the C – SiH 3 oxidative additions as well as the 1,3-shift of methyl and silyl groups show significant differences. The C – CH 3 oxidative addition is highly endothermic (21.7 kcal/mol) and thermodynamically disfavored as it require a Δ G ‡ of 42.2 kcal/mol. On the other hand, the C – SiH 3 oxidative addition is the least endothermic (6.4 kcal/mol) and it requires a moderate Δ G ‡ of 19.6 kcal/mol. Further, the 1,3-SiH 3 migration is the most favored reaction among all the reactions studied here as it proceed with a Δ G ‡ of 13.3 kcal/mol. The small Δ G ‡ for C – SiH 3 oxidative addition and the 1,3-SiH 3 migration are well explained based on the hypervalent character of silicon atom in the corresponding transition states as evidenced from their geometric and LMO features.

High-pressure methods as a tool in organometallic syntheses: facilitation of oxidative addition to platinum(II)

1996 ◽  
Vol 74 (11) ◽  
pp. 1998-2001 ◽  
Author(s):  
Andrew R.L. Skauge ◽  
Richard D. Shalders ◽  
Thomas W. Swaddle
Keyword(s):  
High Pressure ◽  
Pressure Dependence ◽  
Pressure Range ◽  
Oxidative Addition ◽  
Activation Process ◽  
Batch Reactors ◽  
Oxidative Additions ◽  
Solvation Of Ions ◽  
Alkyl Iodides ◽  
Kinetics Of

High-pressure (2 GPa) batch reactors now commercially available may offer substantial accelerations of organometallic syntheses, without resort to heating, when the activation process is multicentered or involves the generation and solvation of ions. As an example of the latter class of reactions, the kinetics of the oxidative additions of methyl and ethyl iodides (RI) to dimethyl(2,2′-bipyridine)platinum(II) in acetone have been studied over the pressure range 0–200 MPa. The volumes of activation ΔV1≠, if assumed to be constant over this range, are −11.7 ± 0.3 and −9.7 ± 0.7 cm3 mol−1, respectively, implying an acceleration of ca. 3000-fold for a batch synthesis of this sort at 2 GPa. However, a possible slight pressure dependence of ΔV1≠ may reduce this acceleration to ca. 1 000-fold. The ΔV1≠ data and the 500-fold retardation on going from R = Me to R = Et are consistent with an SN2 attack of Pt11 on the α-carbon in the alkyl iodides, forming I− and [RMe2Pt(bpy)]+. Key words: volumes of activation, high pressure, oxidative addition, platinum(II), organometallic syntheses.

Some Problems in the Oxidative Addition and Binding of an Ethylene to a Transition Metal Center.

1987 ◽  
Vol 6 (4) ◽  
pp. 902-902
Author(s):  
Jerome Silestre ◽  
Maria Calhorda ◽  
Roald Hoffman ◽  
Page Stoutland ◽  
Robert Bergman
Keyword(s):  
Transition Metal ◽  
Oxidative Addition ◽  
Metal Center

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>

Stereospecific, Palladium-catalyzed C(sp3)–H Alkenylation and Alkynylation of a Proline Derivative Enabled by 8-Aminoquinoline as a Directing Group

2020 ◽  
Author(s):  
Aleksandra Balliu ◽  
Aaltje Roelofje Femmigje Strijker ◽  
Michael Oschmann ◽  
Monireh Pourghasemi Lati ◽  
Oscar Verho
Keyword(s):  
Carboxylic Acid ◽  
Building Blocks ◽  
Wide Range ◽  
Palladium Catalyzed ◽  
Directing Group ◽  
High Yields ◽  
Vinyl Iodides ◽  
Initial Results

<p>In this preprint, we present our initial results concerning a stereospecific Pd-catalyzed protocol for the C3 alkenylation and alkynylation of a proline derivative carrying the well utilized 8‑aminoquinoline directing group. Efficient C–H alkenylation was achieved with a wide range of vinyl iodides bearing different aliphatic, aromatic and heteroaromatic substituents, to furnish the corresponding C3 alkenylated products in good to high yields. In addition, we were able show that this protocol can also be used to install an alkynyl group into the pyrrolidine scaffold, when a TIPS-protected alkynyl bromide was used as the reaction partner. Furthermore, two different methods for the removal of the 8-aminoquinoline auxiliary are reported, which can enable access to both <i>cis</i>- and <i>trans</i>-configured carboxylic acid building blocks from the C–H alkenylation products.</p>

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