Oxidative addition of water to transition metal complexes

Ozerov, Oleg V.

doi:10.1039/b802420k

Cited by 97 publications

(99 citation statements)

References 34 publications

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“…As mentioned in the introduction, there are several known mechanisms for water activation, including (1) oxidative addition to a single transition metal center, a binuclear transition metal center, or a geometrically constrained main group element, (2) O−H cooperative cleavage by a transition metal and its supporting ligands, and (3) coordination‐induced weakening of O−H bonds to form H 2(g) . In the current system, we found that O−H bonds of water were cleaved through a unique ligand–ligand cooperation fashion.…”

Section: Methodsmentioning

confidence: 99%

Activation of O−H and C−O Bonds in Water and Methanol by a Vanadium‐Bound Thiyl Radical

Yan

Yang

Chen

et al. 2018

Chemistry A European J

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The reaction of [V(PS3")] (1) (PS3"=[P(C H -3-Me Si-2-S) ] ) with H O led to the formation of [V (PS3")(PS2"S )] (2) (PS2"S =[P(C H -3-Me Si-2-S) (C H -3-Me Si-2-SH)] ), indicating a hydrogen atom transfer from H O to a bound thiolate in 1. Furthermore, the reaction of 1 with CH OH gave the generation of complexes 2 and 3, [V (PS3")(PS2"S )] (PS2"S =[P(C H -3-Me Si-2-S) (C H -3-Me Si-2-SCH )] ), implying that C-O and O-H bonds are cleaved by 1. Quantum mechanical calculations were performed to provide the mechanistic understanding for the reactivity of 1 with water. A key transition state with a lower kinetic barrier is identified. It involves an O-H bond cleavage by a dissociated thiyl radical with an interaction between an OH group and a neighboring bound sulfur donor. To our knowledge, the reactivity of 1 represents a new mode for water activation conducted through cooperation between a metal-stabilized thiyl radical and a neighboring thiolato donor.

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Section: Methodsmentioning

confidence: 99%

Activation of O−H and C−O Bonds in Water and Methanol by a Vanadium‐Bound Thiyl Radical

Yan

Yang

Chen

et al. 2018

Chemistry A European J

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“…We selected a new type of pincer catalyst ( 3 in Scheme ) recently developed by Milstein and co‐workers12 as a template to derive TM‐free analogues. Such TM pincer catalysts have intriguing electronic structures13 (see below) and exhibit high σ‐bond activation reactivity (e.g., involving HH,12a, b CH,12b NH,14a and OH12d, 14b bonds). They promote the direct synthesis of amides and imines from alcohols and amines12c, e, f as well as the sunlight‐driven splitting of water into dioxygen and dihydrogen 12d.…”

Section: Methodsmentioning

confidence: 99%

Designing Metal‐Free Catalysts by Mimicking Transition‐Metal Pincer Templates

Lü

Zhao

et al. 2011

Chemistry A European J

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Whereas nature often promotes reactions by utilizing cheap and abundant light transition metals (TMs; e.g., Fe, Mn, Ni, Cu, and Zn) in enzyme active sites, the majority of man-made catalysts are based on precious heavy TMs (e.g., Ru, Rh, Ir, Pd, and Pt), despite high costs, limited availability, and contamination problems. Development of cheap, green, and effective catalysts (without precious TMs or even TMs at all) is at the forefront of chemical research. The recent discovery of metal-free reversible hydrogen activation by Stephan and co-workers facilitates direct catalytic hydrogenation.[1] On the basis of the frustrated Lewis pair (FLP) principle, [1,2,3] we designed metal-free hydrogenation catalysts computationally.[4] The metal-free catalyst 1 [4b, c] and the well-known metal-ligand bifunctional hydrogenation catalyst 2 [5] have related electronic and geometric structural features (Scheme 1). Indeed, increasing experimental evidence demonstrates the resemblance between the reactivity of TM-free compounds and TM complexes.[6] Herein, we computationally explore the design of metal-free catalysts by directly mimicking TM catalysts.The M05-2X DFT functional [7] was specifically developed to target nonbonding interactions. We previously calibrated the good performance of the functional [8] in describing weak bonding interactions and applied it to understand the catalytic role of N-heterocyclic carbenes in the metal-free transformation of carbon dioxide into methanol.[9] In our design of FLP-based hydrogen-activation molecules [4a] and hydrogenation catalysts, [4b] we found that the energetic results given by M05-2X were in good agreement with those provided by CCSD(T) [4a] or MP2 calculations.[4b] M05-2X (as implemented in the Gaussian 03 program) [10] was thus selected for use in all of the DFT calculations. All of the geometries were optimized and characterized as minima or transition states (TSs) at the M05-2X/6-31GA C H T U N G T R E N N U N G (d,p) level. The energies were then refined by using M05-2X/6-311 p) wave functions of the TSs were confirmed to be stable, which indicates the reliability of our single-referencebased calculations. The harmonic frequencies at the same level were employed for zero-point energy corrections and thermal and entropy corrections at 298.15 K and 1 atm. Bulky solvation effects were simulated by using the IEFPCM model [11] with benzene as a representative solvent. The corresponding free energies are discussed below, unless otherwise specified. For clarity, we use Lewis structure drawings to depict the electronic structures of molecules in the main text. The optimized geometries and their Cartesian coordinates are provided in the Supporting Information.We selected a new type of pincer catalyst (3 in Scheme 2) recently developed by Milstein and co-workers [12] as a template to derive TM-free analogues. Such TM pincer catalysts have intriguing electronic structures [13] (see below) and exhibit high s-bond activation reactivity (e.g., involving H À H, [12a, b] C À H, [12b]...

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“…First, the bond dissociation energy of the O-H bond in water is 499 kJ⋅mol -1 , which makes this bond one of the strongest X-H interactions. Second, the strength of the newly formed M-H and M-OH bonds should be sufficient to compensate for the rupture of the water molecule (Ozerov 2009). In this context, it is sensible to elucidate the different modes of water addition to metal centres (Scheme 1).…”

Section: Elementary Stepsmentioning

confidence: 98%

Organometallic water splitting – from coordination chemistry to catalysis

Klahn

Beweries

2014

Reviews in Inorganic Chemistry

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AbstractThis review gives an overview on the recent developments in the field of coordination chemistry of water at transition metal centres, which could give implications for a better understanding of the elementary steps of light-driven overall water splitting. Additionally, selected examples for homogeneous catalyst systems that are capable of producing hydrogen and/or oxygen from water are presented, focussing on the mechanistic aspects of water reduction and water oxidation.

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Oxidative addition of water to transition metal complexes

Abstract: Possible modes of reactivity of water with transition metal complexes are analysed and examples of oxidative addition of water are discussed in this tutorial review.

Cited by 97 publications

References 34 publications

Activation of O−H and C−O Bonds in Water and Methanol by a Vanadium‐Bound Thiyl Radical

Activation of O−H and C−O Bonds in Water and Methanol by a Vanadium‐Bound Thiyl Radical

Designing Metal‐Free Catalysts by Mimicking Transition‐Metal Pincer Templates

Organometallic water splitting – from coordination chemistry to catalysis

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