Co(i) complexes with a tetradentate phenanthroline-based PNNP ligand as a potent new metal–ligand cooperation platform

2020 ◽  
Vol 49 (41) ◽  
pp. 14592-14597
Author(s):  
Nai-Yuan Jheng ◽  
Yusuke Ishizaka ◽  
Yuki Naganawa ◽  
Akira Sekiguchi ◽  
Yumiko Nakajima
Keyword(s):  
Bond Cleavage ◽  
Metal Ligand

A cobalt(i) alkyl complex bearing a tetradentate phenanthroline-based PNNP ligand undergoes dearomatization of the ligand backbone skeleton upon heating and furthermore achieves H–H bond cleavage.

B–H Bond Cleavage via Metal–Ligand Cooperation by Dearomatized Ruthenium Pincer Complexes

2014 ◽  
Vol 33 (14) ◽  
pp. 3716-3726 ◽  
Author(s):  
Aviel Anaby ◽  
Burkhard Butschke ◽  
Yehoshoa Ben-David ◽  
Linda J. W. Shimon ◽  
Gregory Leitus ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
Pincer Complexes ◽  
Metal Ligand

Azo NN Bond Cleavage with a Redox-Active Vanadium Compound Involving Metal-Ligand Cooperativity

2012 ◽  
Vol 124 (22) ◽  
pp. 5482-5486 ◽  
Author(s):  
Carsten Milsmann ◽  
Zoë R. Turner ◽  
Scott P. Semproni ◽  
Paul J. Chirik
Keyword(s):  
Bond Cleavage ◽  
Vanadium Compound ◽  
Redox Active ◽  
Metal Ligand

Azo NN Bond Cleavage with a Redox-Active Vanadium Compound Involving Metal-Ligand Cooperativity

2012 ◽  
Vol 51 (22) ◽  
pp. 5386-5390 ◽  
Author(s):  
Carsten Milsmann ◽  
Zoë R. Turner ◽  
Scott P. Semproni ◽  
Paul J. Chirik
Keyword(s):  
Bond Cleavage ◽  
Vanadium Compound ◽  
Redox Active ◽  
Metal Ligand

Femtochemistry of organometallics: dynamics of metal-metal and metal-ligand bond cleavage in M2(CO)10

1995 ◽  
Vol 233 (5-6) ◽  
pp. 500-508 ◽  
Author(s):  
Sang Kyu Kim ◽  
Soren Pedersen ◽  
Ahmed H. Zewail
Keyword(s):  
Bond Cleavage ◽  
Metal Metal ◽  
Metal Ligand ◽  
Ligand Bond

Metal–ligand cooperative C–O bond cleavage of propargylic alcohol with protic pyrazole complexes of ruthenium

2019 ◽  
Vol 220 ◽  
pp. 364-375
Author(s):  
Naoto Tashima ◽  
Satomi Ohta ◽  
Shigeki Kuwata
Keyword(s):  
Bond Cleavage ◽  
Ruthenium Complexes ◽  
Propargylic Alcohol ◽  
Metal Ligand

Protic pyrazole–ruthenium complexes promoted the C–O and C–H bond cleavage of a propargylic alcohol through metal–ligand cooperation.

Metal-Metal Cooperative Bond Activation by Heterobimetallic Alkyl, Aryl, and Acetylide PtII/CuI Complexes

2020 ◽  
Author(s):  
Shubham Deolka ◽  
Orestes Rivada Wheelaghan ◽  
Sandra Aristizábal ◽  
Robert Fayzullin ◽  
Shrinwantu Pal ◽  
...  
Keyword(s):  
Alkyl Group ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Terminal Alkyne ◽  
Alkyl Aryl ◽  
Metal Metal ◽  
The Stability ◽  
Selective Formation ◽  
Organoplatinum Compounds

We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H 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.

Electron Donation by Low-Crystalline Ba-La-Ce Oxygen-Deficient Composite Oxide Accumulating on Ru Nanoparticles for Ammonia Synthesis under Mild Conditions

2019 ◽  
Author(s):  
Katsutoshi Sato ◽  
Shin-ichiro Miyahara ◽  
Yuta Ogura ◽  
Kotoko Tsujimaru ◽  
Yuichiro Wada ◽  
...  
Keyword(s):  
Ammonia Synthesis ◽  
Bond Cleavage ◽  
Synthesis Process ◽  
Strong Electron ◽  
Mild Conditions ◽  
Ru Nanoparticles ◽  
Rate Determining Step ◽  
Highly Active ◽  
Composite Oxides ◽  
Low Crystalline

<p>To mitigate global problems related to energy and global warming, it is helpful to develop an ammonia synthesis process using catalysts that are highly active under mild conditions. Here we show that the ammonia synthesis activity of Ru/Ba/LaCeO<i><sub>x</sub></i> pre-reduced at 700 °C is the highest reported among oxide-supported Ru catalysts. Our results indicate that low crystalline oxygen-deficient composite oxides, which include Ba<sup>2+</sup>, Ce<sup>3+</sup> and La<sup>3+</sup>, with strong electron-donating ability, accumulate on Ru particles and thus promote N≡N bond cleavage, which is the rate determining step for ammonia synthesis.</p>

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