Elucidation of the Wide Range of Reaction Pathways That Accompany the Electrochemical Oxidation ofcis,mer-[Mn(CO)2(η1-dpm)(η2-dpm)X] (dpm = Ph2PCH2PPh2; X = Cl, Br)

Eklund, John C.; Bond, Alan M.; Colton, R.; Humphrey, David; Mahon, Peter J.; Walter, Jacky N.

doi:10.1021/ic980796r

Cited by 8 publications

(11 citation statements)

References 32 publications

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“…Space limitations do only allow a rather selective discussion. For further information, the reader is referred to review articles [13,[18][19][20][21][22][23][24].…”

Section: Scope Of the Chaptermentioning

confidence: 99%

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Linear Sweep and Cyclic Voltammetry

Speiser

2003

Encyclopedia of Electrochemistry

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The sections in this article are Introduction Historical Background Potential Scan Voltammetries—Definitions Scope of the Chapter Theory of Potential Scan Voltammetries General Reversible Electron Transfer Kinetics of Electron Transfer Coupled Homogeneous Chemical Kinetics Adsorption and Surface‐Bound Redox Species Nonlinear Diffusion Restricted Diffusion Simulation Practical Considerations Electrodes and Cells Solvents and Supporting Electrolytes Experimental Limitations Artifacts and how to Avoid Them Present Methodological Developments Voltammetry at Ultramicroelectrodes Fast Scan Techniques Voltammetry without Supporting Electrolyte Voltammetry Under Hydrodynamic Conditions Voltammetric Spectroelectrochemistry Derivative Voltammetry Semiintegral (“Convolution”) and Semiderivative Voltammetry Applications Typical Voltammograms—Classical Applications Selected Recent Examples Conclusion Acknowledgments

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“…Space limitations do only allow a rather selective discussion. For further information, the reader is referred to review articles [13,[18][19][20][21][22][23][24].…”

Section: Scope Of the Chaptermentioning

confidence: 99%

“…Hydrodynamic voltammetry is advantageous in studying processes (heterogeneous electron transfer, homogeneous kinetics) that are faster than mass transport under usual CV or LSV conditions. A recent review provides several examples [22].…”

Section: Voltammetry Under Hydrodynamic Conditionsmentioning

confidence: 99%

Linear Sweep and Cyclic Voltammetry

Speiser

2003

Encyclopedia of Electrochemistry

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“…(i) Cyclic Voltammetry. The oxidation of cis,mer -Mn(CO) 2 (κ 1 -dpm)(κ 2 -dpm)X has been reported in detail elsewhere …”

Section: Resultsmentioning

confidence: 99%

Electron Transfer and Chemical Reactions Associated with the Oxidation of an Extensive Series of Mononuclear Complexes [M(CO)₂(κ¹-P-P)(κ²-P-P)X] and Binuclear Complexes [{M(CO)₂(κ²-P-P)X}₂(μ-P-P)] (M = Mn, Re; P-P = Diphosphine or Related Ligand; X = Cl, Br)

et al. 2004

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The electrochemical oxidation of an extensive series of cis,mer-M(CO) 2 (κ 1 -dpm)(κ 2 -P-P)X (M ) Mn, Re; dpm ) Ph 2 PCH 2 PPh 2 ; P-P ) dpm, Ph 2 PCH 2 CH 2 PPh 2 (dpe), o-(Ph 2 P) 2 C 6 H 4 -(dpbz); X ) Cl, Br) complexes has been investigated on both the voltammetric and bulk electrolysis time scales. At short time domains or low temperatures, the manganese complexes undergo a reversible one-electron oxidation to cis,mer-[Mn(CO) 2 (κ 1 -dpm)(κ 2 -P-P)X] + . These compounds isomerize under slow scan rate voltammetric conditions at room temperature to give trans-[Mn(CO) 2 (κ 1 -dpm)(κ 2 -P-P)X] + , which on even longer bulk electrolysis time scales slowly lose Xto form a reactive trans-[Mn(CO) 2 (κ 2 -dpm)(κ 2 -P-P)] 2+ intermediate. In turn, this complex is reduced either at the electrode surface (X ) Cl) or in a homogeneous chemical reaction (X ) Br) to form trans-[Mn(CO) 2 (κ 2 -dpm)(κ 2 -P-P)] + , which is the final product observed under conditions of bulk electrolysis. In contrast, the first oxidation step for the corresponding rhenium complexes involves oxidation of the pendant phosphorus atom and reaction with traces of water to give cis,mer-Re(CO) 2 (κ 1 -dpmO)(κ 2dpm)X and then cis-[Re(CO) 2 (κ 2 -dpmO) 2 ] + , with the rhenium center subsequently being oxidized at more positive potentials. Methylation of the pendant phosphorus of cis,mer-Re-(CO) 2 (κ 1 -dpm)(κ 2 -dpm)X gives cis,mer-[Re(CO) 2 (κ 1 -dpmMe)(κ 2 -dpm)X] + . The ligand-based oxidation pathway is blocked by the methylation, so that only the usual metal-centered Re-(I)/Re(II)-based oxidation processes are observed in the voltammetry of these compounds. The compounds cis,mer-Re(CO) 2 (κ 1 -ape)(κ 2 -ape)X and cis,mer-[Re(CO) 2 (κ 1 -apeMe)(κ 2 -ape)X] + (ape ) Ph 2 AsCH 2 CH 2 PPh 2 ) exhibit electrochemistry similar to that of the dpm analogues. The major products of the interaction of dpe with the metal pentacarbonyl halides (2:1) are the new binuclear species {M(CO) 2 (κ 2 -dpe)X} 2 (µ-dpe), whose structures have been determined by IR and 31 P NMR spectroscopy and electrospray mass spectrometry (ESMS). The stereochemistry of the manganese complexes is cis,fac, and upon voltammetric oxidation, first one and then the second manganese atom are oxidized. Bulk oxidative electrolysis at low temperature leads to the generation of cis,fac-[{Mn(CO) 2 (κ 2 -dpe)X} 2 (µ-dpe)] + and cis,fac-[{Mn(CO) 2 (κ 2 -dpe)X} 2 (µ-dpe)] 2+ . The stereochemistry of the oxidized metal centers isomerizes to trans + at room temperature, but the binuclear structure is retained. Bulk reductive electrolysis at low temperature after bulk oxidative electrolysis at room temperature leads to the characterization of trans-{Mn(CO) 2 (κ 2 -dpe)X} 2 (µ-dpe). The binuclear rhenium complexes cis,mer-{Re(CO) 2 (κ 2 -P-P)X} 2 (µ-P-P) (P-P ) dpe, Ph 2 P(CH 2 ) 3 PPh 2 (dpp)) were isolated, and they each undergo two successive one-electron oxidations to generate the monoand dications without any isomerization on the voltammetric time scale. ESMS provides independent proof of the bin...

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“…The solid-state photovoltammetry of cis,mer -Mn(CO) 2 (η 1 -dpm)(η 2 -dpm)Br adhered to an electrode in contact with 0.1 M aqueous NaCl was therefore examined. The organic solvent solution-phase voltammetry of interest for this species consists of the one-electron oxidation process, A cis-fac -[Mn(CO) 2 (η 1 -dpm)(η 2 -dpm)Br] + intermediate may also be relevant to the isomerization reaction in eq 4. It can be seen from Figure that significant photocatalysis is observed for electrochemical oxidation of cis,mer -Mn(CO) 2 (η 1 -dpm)(η 2 -dpm)Br in the presence of 300−450 nm UV/visible irradiation, the wavelength of which corresponds to a cis,mer -Mn(CO) 2 (η 1 -dpm)(η 2 -dpm)Br charge-transfer band (λ max = 398 nm in acetonitrile solution).…”

Section: Resultsmentioning

confidence: 99%

Photocatalytic Reactions at Microcrystalline fac-Mn(CO)₃(η²-Ph₂PCH₂PPh₂)Cl−Electrode−Aqueous (Electrolyte) Interfaces

Eklund

Bond

1999

J. Am. Chem. Soc.

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The electrochemical oxidation of fac-Mn(CO)3(η2-dpm)Cl (dpm = Ph2PCH2PPh2) is extensively photocatalyzed when a microcrystal−electrode−aqueous (electrolyte) interface is irradiated with light having a wavelength corresponding to that of the 385 nm charge-transfer band. Investigations of the voltammetry of the solid in the presence and absence of light and monitoring the course of the reaction by EPR, electron probe, and electrochemical quartz crystal microbalance techniques indicate that the catalysis is associated with enhanced charge transport caused by doping of fac-Mn(CO)3(η2-dpm)Cl with photooxidized mer-[Mn(CO)3(η2-dpm)Cl]X, where the anion, X-, is incorporated into the solid after mass transport from the aqueous electrolyte. Photocatalysis also is found for the electrochemical oxidation of cis,mer-Mn(CO)2(η1-dpm)(η2-dpm)Br.

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Elucidation of the Wide Range of Reaction Pathways That Accompany the Electrochemical Oxidation ofcis,mer-[Mn(CO)₂(η¹-dpm)(η²-dpm)X] (dpm = Ph₂PCH₂PPh₂; X = Cl, Br)

Cited by 8 publications

References 32 publications

Linear Sweep and Cyclic Voltammetry

Linear Sweep and Cyclic Voltammetry

Electron Transfer and Chemical Reactions Associated with the Oxidation of an Extensive Series of Mononuclear Complexes [M(CO)₂(κ¹-P-P)(κ²-P-P)X] and Binuclear Complexes [{M(CO)₂(κ²-P-P)X}₂(μ-P-P)] (M = Mn, Re; P-P = Diphosphine or Related Ligand; X = Cl, Br)

Photocatalytic Reactions at Microcrystalline fac-Mn(CO)₃(η²-Ph₂PCH₂PPh₂)Cl−Electrode−Aqueous (Electrolyte) Interfaces

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Elucidation of the Wide Range of Reaction Pathways That Accompany the Electrochemical Oxidation ofcis,mer-[Mn(CO)2(η1-dpm)(η2-dpm)X] (dpm = Ph2PCH2PPh2; X = Cl, Br)

Cited by 8 publications

References 32 publications

Linear Sweep and Cyclic Voltammetry

Linear Sweep and Cyclic Voltammetry

Electron Transfer and Chemical Reactions Associated with the Oxidation of an Extensive Series of Mononuclear Complexes [M(CO)2(κ1-P-P)(κ2-P-P)X] and Binuclear Complexes [{M(CO)2(κ2-P-P)X}2(μ-P-P)] (M = Mn, Re; P-P = Diphosphine or Related Ligand; X = Cl, Br)

Photocatalytic Reactions at Microcrystalline fac-Mn(CO)3(η2-Ph2PCH2PPh2)Cl−Electrode−Aqueous (Electrolyte) Interfaces

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Elucidation of the Wide Range of Reaction Pathways That Accompany the Electrochemical Oxidation ofcis,mer-[Mn(CO)₂(η¹-dpm)(η²-dpm)X] (dpm = Ph₂PCH₂PPh₂; X = Cl, Br)

Electron Transfer and Chemical Reactions Associated with the Oxidation of an Extensive Series of Mononuclear Complexes [M(CO)₂(κ¹-P-P)(κ²-P-P)X] and Binuclear Complexes [{M(CO)₂(κ²-P-P)X}₂(μ-P-P)] (M = Mn, Re; P-P = Diphosphine or Related Ligand; X = Cl, Br)

Photocatalytic Reactions at Microcrystalline fac-Mn(CO)₃(η²-Ph₂PCH₂PPh₂)Cl−Electrode−Aqueous (Electrolyte) Interfaces