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>

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>

Reversible oxidative-addition and reductive-elimination of thiophene from a titanium complex and its thermally-induced hydrodesulphurization chemistry

2020 ◽  
Vol 56 (10) ◽  
pp. 1545-1548 ◽  
Author(s):  
Alejandra Gómez-Torres ◽  
J. Rolando Aguilar-Calderón ◽  
Carlos Saucedo ◽  
Aldo Jordan ◽  
Alejandro Metta-Magaña ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Reductive Elimination ◽  
Thermally Induced ◽  
Titanium Complex

The masked Ti(ii) synthon (Ketguan)(η6-ImDippN)Ti (1) undergoes fully reversible oxidative-addition/reductive-elimination with thiophene while also promoting its hydrodesulphurization upon exposure to H2.

Overcrowded aminophospanitrenes: a case study

2017 ◽  
Vol 72 (11) ◽  
pp. 865-871
Author(s):  
Jürgen Tirrée ◽  
Alexander V. Ruban ◽  
Martin Nieger ◽  
Claudia Li ◽  
László Nyulászi ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Ring Opening ◽  
Ring System ◽  
Thermally Induced ◽  
Induced Decomposition

AbstractIn a search for stable phosphinonitrenes generated by thermally induced decomposition of the azidophosphines 8a, b, different cyclodiphosp(V)azene products were generated. While in the case of 8a the expected phosphinonitrene dimer 10 could be obtained, from 8b, which has the sterically more demanding TMP substituents, product 11, was obtained and characterized. DFT calculations have revealed that the primarily formed phosphinonitrene 9b is unstable against loss of TMP˙, and the resulting radical dimerizes to the biradicaloid 1,3-diaza-2,4-diphosphetane-2,4-diyl 13. Compound 13 then dimerizes after ring opening, yielding in the ring system, which provides the final product upon reaction with the starting azidophosphine.

Probing enantioselectivity in rhodium-catalyzed Si–C bond cleavage to construct silicon-stereocenters: a theoretical study

2019 ◽  
Vol 9 (3) ◽  
pp. 646-651 ◽  
Author(s):  
Zhaoyuan Yu ◽  
Tao Zhang ◽  
Ruopeng Bai ◽  
Yu Lan
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Theoretical Study ◽  
Bond Cleavage ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Functional Theory ◽  
Elimination Process

Density functional theory (DFT) calculations indicate that favorable oxidative addition/reductive elimination process from arylrhodium complex determines the enantioselectivity.

DFT modelling of a diphosphane − N-heterocyclic carbene–Rh(i) pincer complex rearrangement: a computational evaluation of the electronic effects in C–P bond activation

2018 ◽  
Vol 47 (8) ◽  
pp. 2662-2669 ◽  
Author(s):  
H.-L. Qin ◽  
J. Leng ◽  
W. Zhang ◽  
E. A. B. Kantchev
Keyword(s):  
Dft Calculations ◽  
Bond Activation ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Electronic Effects ◽  
Complex Rearrangement ◽  
Rate Determining Step ◽  
Computational Evaluation ◽  
Pincer Complex ◽  
Dft Modelling

DFT calculations confirmed that the rearrangement of a PCP-Rh-H pincer to a CCP-Rh-phosphane pincer occured by C–P oxidative addition (ΔG‡ = 29.5 kcal mol−1, rate-determining step), followed by P–H reductive elimination (ΔG‡ = 4.8 kcal mol−1).

Thiophene ring-opening reactions. Direct access to the synthesis of 1,3,4-thiadiazoline-(condenced) pyridone hybrids

Tetrahedron ◽  
2021 ◽  
pp. 131957
Author(s):  
Mohammed M. Abadleh ◽  
Ahmad H. Abdullah ◽  
Firas F. Awwadi ◽  
Mustafa M. El-Abadelah
Keyword(s):  
Ring Opening ◽  
Thiophene Ring ◽  
Direct Access ◽  
Ring Opening Reactions

scholarly journals The role of hypervalent iodine(iii) reagents in promoting alkoxylation of unactivated C(sp3)–H bonds catalyzed by palladium(ii) complexes

2021 ◽  
Author(s):  
Payam Abdolalian ◽  
Samaneh K. Tizhoush ◽  
Kaveh Farshadfar ◽  
Alireza Ariafard
Keyword(s):  
Dft Calculations ◽  
Oxidative Addition ◽  
Hypervalent Iodine

This work uses DFT calculations to explore Pd(ii)-catalysed iodine(iii)-mediated alkoxylation of unactivated C(sp3)–H bonds and reveals how important the isomerization is in triggering the oxidative addition of ArIX2 to Pd(ii).

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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