Olefin Oxygenation by Water on an Iridium Center

Ghatak, Tapas; Sarkar, Mithun; Dinda, Shrabani; Dutta, Indranil; Rahaman, S. M. Wahidur; Bera, Jitendra K.

doi:10.1021/jacs.5b03055

Cited by 31 publications

(22 citation statements)

References 32 publications

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“…[10] More recently,t he syn-nucleophilic attack of an IrÀOH group on one of the double bonds of a1 ,5-cyclooctadiene (cod) ligand was proposed by Bera et al in the preparation of 1-irida-2-oxetane complexes. [11] Regarding the second alternative (anti attack), 2-R-cyclooct-5-enylc omplexes (R = benzyl, allyl) have been prepared by reactions of carbanions (such as RMgCl) with [Ir(cod)(PMe 3 ) 3 ]Cl, whereas 2-indenylcyclooct-5-enyl was directly obtained from the addition of trimethylphosphane to [Ir(cod)(h 5 -indenyl)]. [12] Moreover,n ucleophilic attack of sodium/potassium alkoxides has been only reported for ac ouple of cationic complexes: [Ir(bipy)(cod)(fumaronitrile)]Cl (bipy = 2,2'-bipyridine) and [Ir(cod)(MeBP 3 )]Cl (MeBP 3 = MeC{CH 2 PPh 2 } 3 )d escribed by the groups of Camus [13] and Caulton, [14] respectively.Int his context, it would be interesting if non-deprotonateda lcohols and neutral complexes could be used to form CÀOb onds;t hus avoiding the formation of stoichiometric amountsofi norganic salts.…”

Section: Introductionmentioning

confidence: 99%

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Inner‐Sphere Oxygen Activation Promoting Outer‐Sphere Nucleophilic Attack on Olefins

Abril

Rı́o

López

et al. 2019

Chemistry A European J

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Alkoxylation and hydroxylation reactions of 1,5‐cyclooctadiene (cod) in an iridium complex with alcohols and water promoted by the reduction of oxygen to hydrogen peroxide are described. The exo configuration of the OH/OR groups in the products agrees with nucleophilic attack at the external face of the olefin as the key step. The reactions also require the presence of a coordinating protic acid (such as picolinic acid (Hpic)) and involve the participation of a cationic diolefin iridium(III) complex, [Ir(cod)(pic)2]+, which has been isolated. Independently, this cation is also involved in easy alkoxy group exchange reactions, which are very unusual for organic ethers. DFT studies on the mechanism of olefin alkoxylation mediated by oxygen show a low‐energy proton‐coupled electron‐transfer step connecting a superoxide–iridium(II) complex with hydroperoxide–iridium(III) intermediates, rather than peroxide complexes. Accordingly, a more complex reaction, with up to four different products, occurred upon reacting the diolefin–peroxide iridium(III) complex with Hpic. Moreover, such hydroperoxide intermediates are the origin of the regio‐ and stereoselectivity of the hydroxylation/alkoxylation reactions. If this protocol is applied to the diolefin–rhodium(I) complex [Rh(pic)(cod)], free alkyl ethers ORC8H11 (R=Me, Et) resulted, and the reaction is enantioselective if a chiral amino acid, such as l‐proline, is used instead of Hpic.

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Section: Introductionmentioning

confidence: 99%

“…More recently, the syn ‐nucleophilic attack of an Ir−OH group on one of the double bonds of a 1,5‐cyclooctadiene (cod) ligand was proposed by Bera et al. in the preparation of 1‐irida‐2‐oxetane complexes …”

Section: Introductionmentioning

confidence: 99%

Inner‐Sphere Oxygen Activation Promoting Outer‐Sphere Nucleophilic Attack on Olefins

Abril

Rı́o

López

et al. 2019

Chemistry A European J

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“…Based on the previous research, [62][63][64][65][66] we next investigated the redox properties of the complexes. We selected the complex 1 as the representative of the complexes.…”

Section: Electrochemistrymentioning

confidence: 99%

Half‐sandwich Ir (III) and Rh (III) complexes as catalysts for water oxidation with double‐site

Peng

Liu

Han

et al. 2019

Applied Organom Chemis

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A series of neutral binuclear iridium and rhodium complexes were synthesized based on bis‐imine ligands under mild conditions. These half‐sandwich late transition metal complexes were isolated in good yields and characterized by elemental analysis, 1H NMR, 13C NMR, HR‐MS, and FT‐IR spectroscopies, and the solid state structure of complexes 1 and 2 were further confirmed by single‐crystal X‐ray diffraction. Cyclic voltammetry (CV) characterization indicated that the complex 1 has the best catalyst for water oxidation process with TOF of 0.8 s−1 at low overpotential of 0.325 V in methanol‐phosphate buffer. The proposed double‐site water oxidation mechanism had been also speculated.

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“…Oxidation of Rh(I) complexes to the corresponding Rh(III) complexes with concomitant oxygenation of unsaturated (olefinic) ligands by hydrogen peroxide or oxygen has been reported previously; however, such systems always contained bi-, ter-, or tetradentate nitrogen ligands possessing a combination of pyridyl and alkylamine moieties. [25][26][27] Hence it is worth noting that such a process could be achieved with a much simpler bipyridine type ligand under very mild reaction conditions. The bond distances between Rh and other atoms (Rh-C = 2.053 and 2.056 Å, Rh-N = 1.998 and 2.17 Å, Rh-O = 2.094 Å) were very similar to the previously prepared complexes (see references 25a and 25b).…”

Section: Feature Syn Thesismentioning

confidence: 99%

Synthesis of Phenanthridines via a Rhodium-Catalyzed C–C Bond Cleavage Reaction of Biphenylene with Nitriles

et al. 2016

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The reaction of biphenylene with various nitriles in the presence of catalytic amount of [Rh(cod) 2 BF 4 ]/dppe under microwave irradiation afforded 9-substituted phenanthridines. The reaction with alkyl and aromatic nitriles provided the corresponding 9-substituted phenanthridines in 26-79% isolated yields. The reaction was also carried out with cyanopyridines and it provided heterocyclic compounds with the bipyridine and terpyridine scaffold. The synthesized bipyridine and terpyridine were complexed with [Rh(cod)Cl] 2. The former provided a Rh(III) complex in which the cyclooctadiene moiety was oxidized to the tetrahydrofuran ring, whereas the latter gave a structurally fluxional complex (in solution) with only one pyridine ring coordinated to the rhodium atom.

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Olefin Oxygenation by Water on an Iridium Center

Cited by 31 publications

References 32 publications

Inner‐Sphere Oxygen Activation Promoting Outer‐Sphere Nucleophilic Attack on Olefins

Inner‐Sphere Oxygen Activation Promoting Outer‐Sphere Nucleophilic Attack on Olefins

Half‐sandwich Ir (III) and Rh (III) complexes as catalysts for water oxidation with double‐site

Synthesis of Phenanthridines via a Rhodium-Catalyzed C–C Bond Cleavage Reaction of Biphenylene with Nitriles

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