Effect of an nitrogen-nitrogen chelate ligand on the insertion reactions of carbon monoxide into a manganese-alkyl bond

Alonso, Francisco; Llamazares, Angela; Vivanco, Marilín; Granda, Santiago García; Diaz, Maria R.

doi:10.1021/om00044a023

Cited by 26 publications

(16 citation statements)

References 2 publications

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“…Although rare cases of carbonyl Mn hydrides have been spectroscopically characterized, similar

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CO bands were reported by Riera et al. for the analogous [HMn(bpy)(CO) 3 ] in THF (1989 and 1892 cm −1 ) . We were able to reproduce the literature data by performing the IR‐SEC of [Mn(bpy)(CO) 3 Br] in MeCN with 0.1 m of phenol (Figure S7).…”

Section: Resultssupporting

confidence: 83%

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Local Proton Source in Electrocatalytic CO₂ Reduction with [Mn(bpy–R)(CO)₃Br] Complexes

Franco

Cometto

Nencini

et al. 2017

Chemistry A European J

136

164

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Abstract:The electrochemical behavior of fac- [Mn(pdbpy) (CO)3Br] (pdbpy = 4-phenyl-6-(phenyl-2,6-diol)-2,2'-bipyridine), 1, in acetonitrile under Ar and its catalytic performances for CO2 reduction with added water, 2,2',2''-trifluoroethanol (TFE) and phenol are discussed in detail. Preparative-scale electrolysis experiments, carried out at -1.5 V vs. SCE in CO2-saturated acetonitrile solutions, reveal that the process selectivity is extremely sensitive to the acid strength, providing CO and formate in different faradaic yields. A detailed spectroelectrochemical (IR and UV-Vis) study under Ar and CO2 atmospheres shows that 1 undergoes fast solvolysis; however dimer formation in acetonitrile is suppressed, providing an atypical reduction mechanism in comparison with other reported Mn I catalysts. Spectroscopic evidence of Mn hydride formation supports the existence of different electrocatalytic CO2 reduction pathways. Furthermore, a comparative investigation performed on the new fac-[Mn(ptbpy)(CO)3Br] (ptbpy = 4-phenyl-6-(phenyl-3,4,5-triol)-2,2'-bipyridine) catalyst, 2, bearing a bipyridyl derivative with OH groups in different positions to those in 1, provides complementary information about the role that the local proton source plays during the electrochemical reduction of CO2.

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“…Although rare cases of carbonyl Mn hydrides have been spectroscopically characterized, similar

\overset{ν}{true}

Section: Resultssupporting

confidence: 83%

“…[a] THF as solvent, data from reference . [b] THF as solvent, data from reference ; br=broad peak, sh=shoulder.…”

Section: Resultsmentioning

confidence: 99%

Local Proton Source in Electrocatalytic CO₂ Reduction with [Mn(bpy–R)(CO)₃Br] Complexes

Franco

Cometto

Nencini

et al. 2017

Chemistry A European J

136

164

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“…The associated IR-SEC spectra recorded for the 20 mM MeI case (Figures 4b and S6) show that sweeping beyond À 1.70 V vs Fc + /Fc gives rise to a new set of peaks at 1988 and 1886 cm À 1 , matching those reported for MnMe. [16] In comparison, the 5 mM MeI case gives rise to peaks matching a mixture of MnMe and Mn 2 in agreement with the less efficient trapping of Mn À seen in cyclic voltammetry. With the aim of converting Mn À quantitatively to MnMe on preparative scale, we electrolyzed MnBr (9.8 mM) fully by passing 2.4 F mol À 1 of charge in presence of MeI (70 mM; 7.1 equiv.)…”

Section: Resultssupporting

confidence: 61%

“…( 10), Scheme 3] acknowledging that this methylating agent is known to provide the methylated manganese complex, MnMe, in a reaction with already generated sodium salt of Mn À . [16] Figure 4a displays cyclic voltammograms of MnBr (1.1 mM) in presence of increasing concentrations of MeI, revealing distinct increases in the absolute electron stoichiometry of the first reduction peak going from 1 to 1.8 at 5 mM MeI (4.5 equiv.) and further to 2.0 at 20 mM MeI (18 equiv.).…”

Section: Resultsmentioning

confidence: 99%

Mechanistic Elucidation of Dimer Formation and Strategies for Its Suppression in Electrochemical Reduction of Fac‐Mn(bpy)(CO)₃Br

et al. 2021

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Development of new catalytic approaches for reduction of small molecules is an aspiring technology to alleviate increasing energy demands without use of fossil fuels. One of the most promising molecular catalysts for reduction of CO 2 is fac-Mn(bpy)(CO) 3 Br (bpy = 2,2'-bipyridine). In this work, the mechanism of electrochemical reduction of this complex is elucidated using cyclic voltammetry along with digital simulations. It is revealed that the dimer complex, Mn 2 (bpy) 2 (CO) 6 , is not, as often assumed, formed by dimerization of the singly reduced manganese complex, [Mn(bpy)(CO) 3 ] * , but instead from its reduction to [Mn(bpy)(CO) 3 ] À , followed by further reaction with Mn(bpy)(CO) 3 Br (rate constant = 1.75 × 10 5 M À 1 s À 1 ). On the basis of cyclic voltammetry, infrared-spectroelectrochemistry, and 1 H NMR spectroscopy, we establish that this parent-child reaction involving Mn(bpy)(CO) 3 Br as electrophile can be diverted by adding either acids or iodomethane as substituting electrophiles. This demonstrates that [Mn(bpy)(CO) 3 ] À , which is the central catalyst for CO 2 reduction, can be formed at less extreme potentials than previously believed by suppressing the parent-child reaction.

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“…The complexes Re(R)(CO)3(R'-DAB) (R,R' = Me, ipr; Et, 'Pr; Bz, 'Pr; Me, tBu; Et, tBu; Bz, tBu; Me, pAn) were all prepared by a modified procedure based on that described by Garcla Alonso et al [17]. To a solution of 0.5 mmol Re(Br)(CO)3(R'-DAB) [18] in 50 ml of THF was added an excess of Na2.…”

Section: Preparation Of the Complexesmentioning

confidence: 99%

Synthesis and spectroscopic properties of Re(R)(CO)3(α-diimine) (R  alkyl; α-diimine  R′-pyCa, R′-DAB) complexes. Crystal structure of Re(Me) (CO)3 (iPr-DAB)

Rossenaar

Kleverlaan

Ven

et al. 1995

Journal of Organometallic Chemistry

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Effect of an nitrogen-nitrogen chelate ligand on the insertion reactions of carbon monoxide into a manganese-alkyl bond

Cited by 26 publications

References 2 publications

Local Proton Source in Electrocatalytic CO₂ Reduction with [Mn(bpy–R)(CO)₃Br] Complexes

Local Proton Source in Electrocatalytic CO₂ Reduction with [Mn(bpy–R)(CO)₃Br] Complexes

Mechanistic Elucidation of Dimer Formation and Strategies for Its Suppression in Electrochemical Reduction of Fac‐Mn(bpy)(CO)₃Br

Synthesis and spectroscopic properties of Re(R)(CO)3(α-diimine) (R  alkyl; α-diimine  R′-pyCa, R′-DAB) complexes. Crystal structure of Re(Me) (CO)3 (iPr-DAB)

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Effect of an nitrogen-nitrogen chelate ligand on the insertion reactions of carbon monoxide into a manganese-alkyl bond

Cited by 26 publications

References 2 publications

Local Proton Source in Electrocatalytic CO2 Reduction with [Mn(bpy–R)(CO)3Br] Complexes

Local Proton Source in Electrocatalytic CO2 Reduction with [Mn(bpy–R)(CO)3Br] Complexes

Mechanistic Elucidation of Dimer Formation and Strategies for Its Suppression in Electrochemical Reduction of Fac‐Mn(bpy)(CO)3Br

Synthesis and spectroscopic properties of Re(R)(CO)3(α-diimine) (R  alkyl; α-diimine  R′-pyCa, R′-DAB) complexes. Crystal structure of Re(Me) (CO)3 (iPr-DAB)

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Local Proton Source in Electrocatalytic CO₂ Reduction with [Mn(bpy–R)(CO)₃Br] Complexes

Local Proton Source in Electrocatalytic CO₂ Reduction with [Mn(bpy–R)(CO)₃Br] Complexes

Mechanistic Elucidation of Dimer Formation and Strategies for Its Suppression in Electrochemical Reduction of Fac‐Mn(bpy)(CO)₃Br