Metal/Ligand Proton Tautomerism Facilitates Dinuclear H2 Reductive Elimination

2020 ◽  
Vol 142 (51) ◽  
pp. 21439-21449
Author(s):  
Jonathan L. Kuo ◽  
Karen I. Goldberg
Keyword(s):  
Reductive Elimination ◽  
Metal Ligand

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>

S(IV)–Mediated Unsymmetrical Heterocycle Cross-Couplings

2019 ◽  
Author(s):  
Min Zhou ◽  
Jet Tsien ◽  
Tian Qin
Keyword(s):  
Cross Coupling ◽  
Reductive Elimination ◽  
Facile Synthesis ◽  
Trigonal Bipyramidal

<p>Herein we report a sulfur (IV) mediated cross-coupling for facile synthesis of heteroaromatic substrates. Addition of heteroaryl nucleophiles onto a simple, readily-accessible alkyl sulfinyl (IV) chloride allows formation of a trigonal bipyramidal sulfurane intermediate. Reductive elimination therefrom provides bis-heteroaryl products in a practical and efficient fashion. <br></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>

ESTIMATING THE STABILITY OF METAL–LIGAND BONDING IN CARBOXYL-CONTAINING POLYMER COMPLEXES BY IR SPECTROSCOPY

2020 ◽  
Vol 61 (12) ◽  
pp. 1876-1887
Author(s):  
T. V. Berestova ◽  
K. N. Nosenko ◽  
O. V. Lusina ◽  
L. G. Kuzina ◽  
E. I. Kulish ◽  
...  
Keyword(s):  
Ir Spectroscopy ◽  
Polymer Complexes ◽  
The Stability ◽  
Metal Ligand

A Solvent-Dependent and Electrochemically Controlled Self-Assembling/Disassembling System

2003 ◽  
Vol 68 (9) ◽  
pp. 1647-1662 ◽  
Author(s):  
Valeria Amendola ◽  
Massimo Boiocchi ◽  
Yuri Diaz Fernandez ◽  
Carlo Mangano ◽  
Piersandro Pallavicini
Keyword(s):  
Equilibrium Mixture ◽  
Bidentate Ligand ◽  
Molecular Structures ◽  
The Self ◽  
Molar Ratio ◽  
Crystal And Molecular Structures ◽  
Self Assembling ◽  
Irreversible Oxidation ◽  
Irreversible Reduction ◽  
Metal Ligand

The bis-bidentate ligand R,S-1,2-diphenyl-N,N'-bis(2-quinolinemethylidene)ethane-1,2-diamine (ligand 4), containing two (iminomethyl)quinoline moieties separated by a cis-1,2-diphenylethylene spacer, forms stable complexes with both CuI and CuII. With CuII, the monomeric 1:1 complex [CuII(4)]2+ is obtained both in CH3CN and CH2Cl2. With CuI and overall 1:1 metal/ligand molar ratio, an equilibrium mixture is obtained in CH3CN, consisting of [CuI(4)2]+, [CuI2(4)2]2+ and [CuI2(4)(CH3CN)4]2+. The preponderant species is the two-metal one-ligand "open" complex [CuI2(4)(CH3CN)4]2+, in which each Cu+ cation is coordinated in a tetrahedral fashion by one (iminomethyl)quinoline unit and by two CH3CN molecules. Precipitation from the equilibrium mixture yields only crystals of [CuI2(4)(CH3CN)4](ClO4)2·2CH3CN, whose crystal and molecular structures have been determined. On the other hand, in the poorly coordinating CH2Cl2 solvent, only the dimeric helical [CuI2(4)2]2+ complex is obtained, when the overall metal/ligand 1:1 molar ratio is chosen. Addition of large quantities of acetonitrile to solutions of [CuI2(4)2]2+ in dichlorometane results in the formation of [CuI2(4)(CH3CN)4]2+, i.e. in the solvent-driven disassembling of the CuI helicate. While electrochemistry in CH3CN is poorly defined due to the presence of more than one CuI species, cyclic voltammetry experiments carried out in CH2Cl2 revealed a well defined behavior, with irreversible oxidation of [CuI2(4)2]2+ and irreversible reduction of [CuII(4)]2+ taking place at separate potentials (∆E ≈ 700 mV). Irreversibility and separation of the redox events are due to the self-assembling and disassembling processes following the reduction and oxidation, respectively.

scholarly journals Self-Assembled Nanomaterials Based on Complementary Sn(IV) and Zn(II)-Porphyrins, and Their Photocatalytic Degradation for Rhodamine B Dye

Molecules ◽  
2021 ◽  
Vol 26 (12) ◽  
pp. 3598
Author(s):  
Nirmal K. Shee ◽  
Hee-Joon Kim
Keyword(s):  
Aqueous Solution ◽  
Visible Light Irradiation ◽  
Rhodamine B ◽  
Self Assembly ◽  
The Self ◽  
Assembly Process ◽  
Absorption Bands ◽  
Ligand Coordination ◽  
Rhodamine B Dye ◽  
Metal Ligand

A series of porphyrin triads (1–6), based on the reaction of trans-dihydroxo-[5,15-bis(3-pyridyl)-10,20-bis(phenyl)porphyrinato]tin(IV) (SnP) with six different phenoxy Zn(II)-porphyrins (ZnLn), was synthesized. The cooperative metal–ligand coordination of 3-pyridyl nitrogens in the SnP with the phenoxy Zn(II)-porphyrins, followed by the self-assembly process, leads to the formation of nanostructures. The red-shifts and remarkable broadening of the absorption bands in the UV–vis spectra for the triads in CHCl3 indicate that nanoaggregates may be produced in the self-assembly process of these triads. The emission intensities of the triads were also significantly reduced due to the aggregation. Microscopic analyses of the nanostructures of the triads reveal differences due to the different substituents on the axial Zn(II)-porphyrin moieties. All these nanomaterials exhibited efficient photocatalytic performances in the degradation of rhodamine B (RhB) dye under visible light irradiation, and the degradation efficiencies of RhB in aqueous solution were observed to be 72~95% within 4 h. In addition, the efficiency of the catalyst was not impaired, showing excellent recyclability even after being applied for the degradation of RhB in up to five cycles.

scholarly journals Force-modulated reductive elimination from platinum(ii) diaryl complexes

2021 ◽  
Author(s):  
Yichen Yu ◽  
Chenxu Wang ◽  
Liqi Wang ◽  
Cai-Li Sun ◽  
Roman Boulatov ◽  
...  
Keyword(s):  
Transition State ◽  
Reductive Elimination ◽  
Mechanical Force ◽  
Elimination Reactions

The influence of mechanical force on the rates of model reductive elimination reactions depends on the structure of the force-transducing ligand and provides a measure of geometry changes upon reaching the transition state.

Mechanistic Study of Metal–Ligand Cooperativity in Mn(II)-Catalyzed Hydroborations: Hemilabile SNS Ligand Enables Metal Hydride-Free Reaction Pathway

ACS Catalysis ◽  
2021 ◽  
pp. 9043-9051
Author(s):  
Matthew R. Elsby ◽  
Mina Son ◽  
Changjin Oh ◽  
Jessica Martin ◽  
Mu-Hyun Baik ◽  
...  
Keyword(s):  
Metal Hydride ◽  
Reaction Pathway ◽  
Mechanistic Study ◽  
Sns Ligand ◽  
Metal Ligand
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