Unexpected Binuclear Bis(phenolato) Titanium (IV) {[(L)Ti(Ph)]2(μ-OEt)2} Assisted by Carbon−Oxygen Bond Cleavage and Alkali-Metal-Containing Titanium(III) Complexes [Ti(L)2·M(solv)2] (M = Li, Na, K; solv = THF, DME)

2007 ◽  
Vol 26 (16) ◽  
pp. 4072-4075 ◽  
Author(s):  
Dao Zhang
Keyword(s):  
Alkali Metal ◽  
Bond Cleavage ◽  
Oxygen Bond

ChemInform Abstract: Carbon-Oxygen Bond-Cleavage Reactions by Electron Transfer. Part 4. Electrochemical and Alkali-Metal Reductions of Phenoxynaphthalenes.

ChemInform ◽  
1989 ◽  
Vol 20 (29) ◽  
Author(s):  
T. A. THORNTON ◽  
G. A. ROSS ◽  
D. PATIL ◽  
K. MUKAIDA ◽  
J. O. WARWICK ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Alkali Metal ◽  
Bond Cleavage ◽  
Cleavage Reactions ◽  
Oxygen Bond

Carbon-oxygen bond-cleavage reactions by electron transfer. 4. Electrochemical and alkali-metal reductions of phenoxynaphthalenes

1989 ◽  
Vol 111 (7) ◽  
pp. 2434-2440 ◽  
Author(s):  
Todd A. Thornton ◽  
Gerald A. Ross ◽  
Dilip Patil ◽  
Kenichi Mukaida ◽  
Jeffrey O. Warwick ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Alkali Metal ◽  
Bond Cleavage ◽  
Cleavage Reactions ◽  
Oxygen Bond

Room Temperature Alkali Metal Reduction of Carbon Dioxide

2020 ◽  
Author(s):  
Lucas A. Freeman ◽  
Akachukwu D. Obi ◽  
Haleigh R. Machost ◽  
Andrew Molino ◽  
Asa W. Nichols ◽  
...  
Keyword(s):  
Alkali Metal ◽  
Alkali Metals ◽  
Room Temperature ◽  
Chemical Reduction ◽  
Bond Cleavage ◽  
Open Shell ◽  
Metal Reduction ◽  
One Pot ◽  
Earth Abundant ◽  
Electron Reduction

The reduction of the relatively inert carbon–oxygen bonds of CO<sub>2</sub> to access useful CO<sub>2</sub>-derived organic products is one of the most important fundamental challenges in synthetic chemistry. Facilitating this bond-cleavage using earth-abundant, non-toxic main group elements (MGEs) is especially arduous because of the difficulty in achieving strong inner-sphere interactions between CO<sub>2</sub> and the MGE. Herein we report the first successful chemical reduction of CO<sub>2</sub> at room temperature by alkali metals, promoted by a cyclic(alkyl)(amino) carbene (CAAC). One-electron reduction of CAAC-CO<sub>2</sub> adduct (<b>1</b>) with lithium, sodium or potassium metal yields stable monoanionic radicals clusters [M(CAAC–CO<sub>2</sub>)]<sub>n</sub>(M = Li, Na, K, <b> 2</b>-<b>4</b>) and two-electron alkali metal reduction affords open-shell, dianionic clusters of the general formula [M<sub>2</sub>(CAAC–CO<sub>2</sub>)]<sub>n </sub>(<b>5</b>-<b>8</b>). It is notable that these crystalline clusters of reduced CO<sub>2</sub> may also be isolated via the “one-pot” reaction of free CO<sub>2</sub> with free CAAC followed by the addition of alkali metals – a reductive process which does not occur in the absence of carbene. Each of the products <b>2</b>-<b>8</b> were investigated using a combination of experimental and theoretical methods.<br>

Oxygen-Oxygen Bond Cleavage and Formation in Co(II) Mediated Stoichiometric O2 Reduction via the Potential Intermediacy of a Co(IV) Oxyl Radical

2018 ◽  
Author(s):  
Lucie Nurdin ◽  
Denis M. Spasyuk ◽  
Laura Fairburn ◽  
Warren Piers ◽  
Laurent Maron
Keyword(s):  
Bond Cleavage ◽  
Peroxo Complex ◽  
Oxygen Oxygen ◽  
O2 Reduction ◽  
Oxygen Bond ◽  
Pentadentate Ligand

Diprotonation of a remarkably stable, toluene soluble cobalt peroxo complex supported by a neutral, dianionic pentadentate ligand leads to facile O-O bond cleavage and production of a highly reactive Co(IV) oxyl cation intermediate that dimerizes and releases O<sub>2</sub>. These processes are relevant to both O<sub>2</sub> reduction and O<sub>2</sub> evolution and the mechanism was probed in detail both experimentally and computationally.

scholarly journals Selective Formation of an FeIV O or an FeIII OOH Intermediate From Iron(II) and H2 O2 : Controlled Heterolytic versus Homolytic Oxygen-Oxygen Bond Cleavage by the Second Coordination Sphere

2018 ◽  
Vol 131 (3) ◽  
pp. 864-868 ◽  
Author(s):  
Khaled Cheaib ◽  
M. Qadri E. Mubarak ◽  
Katell Sénéchal-David ◽  
Christian Herrero ◽  
Régis Guillot ◽  
...  
Keyword(s):  
Coordination Sphere ◽  
Bond Cleavage ◽  
Oxygen Oxygen ◽  
Second Coordination Sphere ◽  
Selective Formation ◽  
Oxygen Bond
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