Palladium(II) p-Tolylamide and Reaction with CO<sub>2</sub>to Generate a Carbamato Derivative

Seul, Jung Min; Park, Soonheum

doi:10.5012/bkcs.2010.31.12.3745

Cited by 8 publications

(5 citation statements)

References 27 publications

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“…The scenario changed over the last 15 years, as several carbamato complexes obtained by this methodology were reported, and especially organometallic species. These include late d-block metals such as iridium [190,191], nickel [192][193][194][195][196][197], palladium [198,199], gold [200] and zinc [201][202][203][204], f-block metals cerium [134] and uranium [205][206][207][208][209] and p-block metals tin [210] and gallium [211,212]. Furthermore, in situ-formed amide complex of Zn(II) and alkyl-amide of Mg(II) were mixed under carbon dioxide atmosphere to afford a heterobimetallic Zn/Mg alkyl-carbamato derivative [213].…”

Section: Heteroleptic Carbamato Complexesmentioning

confidence: 99%

“…Additionally, in this case, a mechanism involving the direct nucleophilic attack of nitrogen to carbon dioxide appears to be favored over a [2 + 2] cycloaddition [185,222]. The cyclic metallacarbamato ligand may undergo further reactions, i.e., a second CO2 insertion to produce a bis-carbamato (azadicarboxylato) ligand Some of the late transition metal complexes featuring a monodentate carbamate are quite unstable towards decarboxylation, either in solution or in the solid state, especially under vacuum [190][191][192]198,200]. Among other factors, the relatively strong metal-nitrogen bond may contribute to the reversibility of the CO 2 insertion process.…”

Section: Heteroleptic Carbamato Complexesmentioning

confidence: 99%

“…Some of the late transition metal complexes featuring a monodentate carbamate are quite unstable towards decarboxylation, either in solution or in the solid state, especially under vacuum [ 190 , 191 , 192 , 198 , 200 ]. Among other factors, the relatively strong metal-nitrogen bond may contribute to the reversibility of the CO 2 insertion process.…”

Section: Synthesis Structure and Reactivity Of Metal Carbamatesmentioning

confidence: 99%

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Recent Advances in the Chemistry of Metal Carbamates

et al. 2020

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Following a related review dating back to 2003, the present review discusses in detail the various synthetic, structural and reactivity aspects of metal species containing one or more carbamato ligands, representing a large family of compounds across all the periodic table. A preliminary overview is provided on the reactivity of carbon dioxide with amines, and emphasis is given to recent findings concerning applications in various fields.

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Section: Heteroleptic Carbamato Complexesmentioning

confidence: 99%

Section: Heteroleptic Carbamato Complexesmentioning

confidence: 99%

Section: Synthesis Structure and Reactivity Of Metal Carbamatesmentioning

confidence: 99%

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Recent Advances in the Chemistry of Metal Carbamates

et al. 2020

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“…Subsequently, there have been a number of reports of CO 2 insertion into pincer-supported group 10 amides 119 – 123 (Figure ). ,− This includes systems with different donors trans to the amide and different substituents on the amide. However, at this stage, there are no quantitative studies assessing how changes in the metal, amide substituents, or ancillary ligand affect the rate of insertion into the metal amide bond.…”

Section: Co2 Insertion Into Metal Amide Bondsmentioning

confidence: 99%

Carbon Dioxide Insertion into Group 9 and 10 Metal–Element σ Bonds

Hazari

Heimann

2017

Inorg. Chem.

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Carbon dioxide (CO 2 ) is an appealing feedstock for the sustainable preparation of a variety of carbon-based commodity chemicals because of its high abundance, low cost, and nontoxicity. The high kinetic and thermodynamic stability of CO 2 , however, means that there are currently only a limited number of practical catalytic systems for the conversion of CO 2 into more valuable chemicals, and continued research in this area is required. One promising approach for the eventual transformation of CO 2 is to initially insert the molecule into transition-metal−element σ bonds such as M−H, M−OR, M−NR 2 , and M−CR 3 bonds to form products of the type M−OC(O)E (E = H, OR, NR 2 , or CR 3 ). CO 2 insertion has been demonstrated in numerous stoichiometric reactions involving transition-metal complexes, but in cases where insertion results in the formation of strong M−O bonds, the products are often too stable to undergo further transformations. Group 9 and 10 transition-metal complexes (M = Ni, Pd, Pt, Co, Rh, or Ir) form relatively weak M−O bonds, and as a consequence, a number of group 9 and 10 transition-metal catalysts in which CO 2 insertion is proposed as an elementary step in catalysis have been developed. In this Award Article, we summarize group 9 and 10 transition-metal complexes in which CO 2 insertion into a metal−element σ bond to form a M−OC(O)E-type product has been observed. Mechanistic similarities and differences are highlighted by comparing CO 2 insertion reactions in different types of group 9 and 10 metal−element σ bonds, and a general trend for predicting the ratedetermining step of the insertion process is described based on the nucleophilicity of the element in the σ bond. Although we focus on stoichiometric reactivity, the relevance of CO 2 insertion to catalytic reactions is also emphasized throughout the paper.

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“…The IR spectrum shows two absorption bands for the N-CO 2 group at ν = 1636 and 1304 cm -1 , which are typical values for the structure illustrated in Scheme 2. [33,35,36] The ν(Fe-Cl) mode is observed at ν = 355 and 340 cm -1 . The elemental and chloro analyses confirmed the insertion of one molecule of CO 2 .…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Chloro‐ and Alkyliron Complexes with N‐Donor Ligands and Their Reactivity towards CO₂

2015

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New iron(II) compounds with N-donor ligands [2,2′-bipyridine (bpy) and 2-(2-pyridyl)ethylamine (pyea)] were synthesized, and their reactivity with carbon dioxide was investigated. The reactions of Fe(bpy)(pyea)Cl2 (1) with CO2 (0.9 MPa) afforded the carbamato derivative Fe(bpy)(pyea-CO2)Cl2 (2), which reacted with CH3Li to afford the monomethyl carbamato complex Fe(bpy)(pyea-CO2)ClCH3 (3), an example of a carbamato species that is stable over a carboxylato moiety. Fe[(bpy)(pyea)](CH3)2 (4), obtained by reaction of 1 with CH3Li, was treated with CO2 (0.3-0.5 MPa) to afford the dicarboxylato species Fe[(bpy)(pyea)](O2CCH3)2 (5), which provides evidence of normal double insertion of CO2 into the Fe-C bond. The reaction of 5 with HCl afforded 1 and CH3-CO2H, which confirmed the mode of bonding of the -O2CCH3 moiety to the Fe center. To verify the preference of insertion of CO2 into the Fe-C or the Fe-N bond, 1 was treated with MeLi (1 equiv.), and Fe(bpy)(pyea)Cl(CH3) (6) was isolated as a low-melting solid. The latter was treated with CO2 (0.5 MPa), and the product of insertion into the Fe-CH3 bond was observed as the only carboxylate (7). The faster insertion into the Fe-CH3 bond is explained by the fact that the N donor is quaternarized upon interaction with the metal center and has no free electrons available to interact with the C acceptor of the cumulene molecule; thus, more-forcing conditions (0.9 MPa) are required for the insertion to occur

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Palladium(II) p-Tolylamide and Reaction with CO₂to Generate a Carbamato Derivative

Cited by 8 publications

References 27 publications

Recent Advances in the Chemistry of Metal Carbamates

Recent Advances in the Chemistry of Metal Carbamates

Carbon Dioxide Insertion into Group 9 and 10 Metal–Element σ Bonds

Synthesis and Characterization of Chloro‐ and Alkyliron Complexes with N‐Donor Ligands and Their Reactivity towards CO₂

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Palladium(II) p-Tolylamide and Reaction with CO2to Generate a Carbamato Derivative

Cited by 8 publications

References 27 publications

Recent Advances in the Chemistry of Metal Carbamates

Recent Advances in the Chemistry of Metal Carbamates

Carbon Dioxide Insertion into Group 9 and 10 Metal–Element σ Bonds

Synthesis and Characterization of Chloro‐ and Alkyliron Complexes with N‐Donor Ligands and Their Reactivity towards CO2

Contact Info

Product

Resources

About

Palladium(II) p-Tolylamide and Reaction with CO₂to Generate a Carbamato Derivative

Synthesis and Characterization of Chloro‐ and Alkyliron Complexes with N‐Donor Ligands and Their Reactivity towards CO₂