Anodic infrared spectroelectrochemistry of mono- and dinuclear complexes containing the (η5-C5H4R) Mn(CO)2L moiety (L = CO or PR3)

Atwood, Christopher G.; Geiger, William E.; Bitterwolf, Thomas E.

doi:10.1016/0022-0728(95)04201-x

Cited by 36 publications

(48 citation statements)

References 39 publications

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“…The average g value of 2.0836 is consistent with the measured fluid solution spectrum, which has g ) 2.0820, with a peak-to-peak width of 20 When a portion of the anodic electrolysis solution containing 3 + was removed for an IR analysis, a band at ν 1964 cm -1 was observed, shifted only 11 cm -1 from ν 1953 cm -1 for the neutral complex 3. Since a small band was also observed at ν 2037 cm -1 , an IR-transparent thin-layer electrochemistry (IRTTLE) experiment 15 was undertaken to clarify the assignments. In this case, electrolysis of 3 at E appl ) 0.1 V resulted in smooth conversion of 3 (ν CO 1953 cm -1 ) to 3 + (ν CO 1964 cm -1 ) without production of IR-active side products ( Figure 3).…”

Section: Resultsmentioning

confidence: 99%

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One-Electron Oxidation of Heterodinuclear Organometallic Compounds Having Polyphosphido Bridges

Winter

Geiger

2003

Organometallics

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The electrochemical behavior of several heterometallic compounds having polyphosphido bridges has been investigated. Reversible one-electron oxidations were observed for Cp*Fe-(P 5)TaCp′′ (2), Cp*Fe(P 5)[Ir 2 (CO) 2 Cp* 2 ] (3), and Cp′′′ 2 Co 2 (P 2) 2 (4) (Cp*) C 5 M 5 , Cp′′) C 5 H 3 t Bu 2 , Cp′′′) C 5 H 2 t Bu 3). In contrast to the pseudo-sandwich polyphosphido complex Cp*FeP 5 (1), compounds 2-4 undergo very facile oxidations and the corresponding monocations may be generated by bulk electrolysis or by reaction with ferrocenium ion. E 1/2 values (vs Cp 2 Fe 0/+) for the oxidations are-0.24 V for 2,-0.58 V for 3, and-0.33 V for 4 in CH 2 Cl 2 /0.1 M [NBu 4 ][PF 6 ], in contrast to 0.57 V for 1. Although ESR spectra of 2 + display hyperfine coupling to 181 Ta, the SOMO appears to have only minor Ta character. IR spectroelectrochemistry of the 3/3 + couple reveals an increase of ν CO of only 11 cm-1 , indicating that the oxidation of 3 also occurs predominantly at the iron center. The fact that the Fe-based oxidations of 2 and 3 are more negative than that of 1 by ca. 0.8 and 1.15 V, respectively, is ascribed to differences in the iron formal oxidation state which arise from the structural variations of the P 5 bridging groups.

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Section: Resultsmentioning

confidence: 99%

“…Infrared thin-layer spectroelectrochemistry (IRTTLE) experiments were conducted as described earlier. 15 Voltammetric diagnostics followed the procedures previously noted; 16 expanded experimental details may be obtained from ref 10.…”

Section: Methodsmentioning

confidence: 99%

One-Electron Oxidation of Heterodinuclear Organometallic Compounds Having Polyphosphido Bridges

Winter

Geiger

2003

Organometallics

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“…Studies of triphenylphosphane-substituted cymantrenyl complexes showed that the thermodynamic and kinetic stabilities of the cationic complexes are greatly enhanced. [9] The effect of employing Fischer carbenes as weaker π-acceptors than carbonyls is herein imposed by synthesizing a series of cymantrene Fischer alkoxycarbene complexes containing heteroaryl (thienyl, Th, or furyl, Fu) substituents. Both the monoand the biscarbene complexes with bridging 2,5-thienylene (Th') or 2,5-furylene (Fu') carbene substituents, were prepared.…”

Section: Introductionmentioning

confidence: 99%

“…This paper addresses the first of these points by substituting one carbonyl ligand with a less π‐accepting ligand, namely, a heteroatom‐substituted carbene ligand. Studies of triphenylphosphane‐substituted cymantrenyl complexes showed that the thermodynamic and kinetic stabilities of the cationic complexes are greatly enhanced 9. The effect of employing Fischer carbenes as weaker π‐acceptors than carbonyls is herein imposed by synthesizing a series of cymantrene Fischer alkoxycarbene complexes containing heteroaryl substituents such as thienyl (Th) or furyl (Fu).…”

Section: Introductionmentioning

confidence: 99%

Redox Behaviour of Cymantrene Fischer Carbene Complexes in Designing Organometallic Multi‐tags

Bezuidenhout

Westhuizen

Swarts

et al. 2014

Chemistry A European J

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All complexes showed that the redox potentials of carbene double bond reduction and Mn(I) oxidation were dependent on the type of Ar group, but only 3b showed resolved oxidations for the two Mn(I) centres. Surprisingly, Mn(I) oxidation occurs at lower potentials than ferrocenyl oxidation. Density functional theory (DFT) calculations were carried out to delineate the nature of the species involved in the oxidation and reduction processes and clearly confirm that oxidation of Mn(I) is favoured over that of ferrocene.

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“…This approach has even been used for protein redox potential measurements using a mediated continuous-flow column electrolytic spectroelectrochemical technique (CFCE-SET) [83,84]. Geiger has used reflection optics for monitoring the solutions of bulkgenerated air-sensitive complexes [85,86].…”

Section: General Considerationsmentioning

confidence: 99%

Spectroelectrochemistry: In s itu UV ‐visible Spectroscopy

Crayston

2003

Encyclopedia of Electrochemistry

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The sections in this article are Introduction and Principles Introductory Remarks Theory and Techniques: Steady State Measurement Cell Transmission for a Simple Electron Transfer Reaction: Determination of E and n Effect of Follow‐up Reactions in OTTLE Cells Theory and Techniques: Kinetic Measurements Chronoabsorptometry Instrumentation for Chronoabsorptometry Slow Heterogeneous Kinetics Effect of Follow‐up Reactions Derivative Cyclic Voltabsorptometry ( DCVA ) Galvanostatic Conditions Adsorption Cell Geometries, Design, Techniques, and Instrumentation General Considerations Transmission under Thin‐layer Conditions: OTTLEs and Flow‐cells Variations on and Alternatives to the Basic OTTLE Design OTTLE Cells Intended for Both UV ‐visible and FTIR Use OTTLE Cell Electrochemical and Spectroscopic Response Semi‐infinite Cells: Optically Transparent Electrodes ( OTEs ) Reflection from Electrodes and Liquid–Liquid Interfaces Glancing Incidence Reflection, Near‐parallel or Parallel Reflection, and Diffraction Liquid–Liquid Interface and Attenuated Total Reflection Long Optical Path‐length Thin‐layer Cell ( LOPTLC ) Forced Convection, RDE and Channel Flow UV ‐vis Combined with Other Spectroscopic Techniques Applications Solution Studies of Inorganic Species Solution Studies of Organic Species Molten Salts Spectroelectrochemistry Studies of Species of Biological Interest Inorganic Thin Films and Modified Electrodes Conducting Polymers and Oligomer Models Conclusions

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Anodic infrared spectroelectrochemistry of mono- and dinuclear complexes containing the (η5-C5H4R) Mn(CO)2L moiety (L = CO or PR3)

Cited by 36 publications

References 39 publications

One-Electron Oxidation of Heterodinuclear Organometallic Compounds Having Polyphosphido Bridges

One-Electron Oxidation of Heterodinuclear Organometallic Compounds Having Polyphosphido Bridges

Redox Behaviour of Cymantrene Fischer Carbene Complexes in Designing Organometallic Multi‐tags

Spectroelectrochemistry: In s itu UV ‐visible Spectroscopy

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