Infrared, conductance, and kinetic evidence for alkali metal ion interactions with derivatives of manganese carbonylates

Darensbourg, Marcetta Y.; Darensbourg, Donald J.; Burns, Drusilla L; Drew, D. A.

doi:10.1021/ja00427a011

Cited by 73 publications

(20 citation statements)

References 6 publications

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“…This difference also cannot be attributed to ion pairing with Na + ions in 1 Na because such interactions would be expected to shift the CO stretching bands to higher energies rather than lower energies. 35 Figure 5 shows a schematic of one possible explanation for this difference. Specifically, while the optical band gaps of 1 Na and 1 Me 3 Si remain the same because of their identical NC sizes, the potentials of the band edges and of the filled surface states of 1 Na are shifted to more negative potentials than those of 1 Me 3 Si because of the electrostatic differences between the NC surfaces.…”

Section: ■ Resultsmentioning

confidence: 99%

“…This difference cannot be attributed to changes to the ligand sphere; the surface OA densities quantified by 1 H NMR spectroscopy between the two samples are similar ( 1 Me 3 Si , 2.3 OA/nm 2 ; 1 Na , 2.6 OA/nm 2 ). This difference also cannot be attributed to ion pairing with Na + ions in 1 Na because such interactions would be expected to shift the CO stretching bands to higher energies rather than lower energies …”

Section: Discussionmentioning

confidence: 98%

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Metal-Carbonyl-Functionalized CdSe Nanocrystals: Synthesis, Surface Redox, and Infrared Intensities

2021

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Characterizing the surfaces of colloidal semiconductor nanocrystals (NCs) remains a key challenge for understanding and controlling their physical properties and chemical behavior. For this reason, the development of new methods to study NC surfaces is of great interest. In this paper, we report the use of (Me 3 Si) 2 Fe(CO) 4 and Et 3 SiCo(CO) 4 as reagents for functionalizing CdSe NC surfaces with organometallic metal tetracarbonyl fragments. This method avoids NC surface reduction and can achieve high metal carbonyl surface densities. Surface reduction or oxidation, as well as changes to the surface stoichiometry, was shown to shift the metal carbonyl CO stretching frequencies, making these surface-bound metal carbonyl fragments useful spectroscopic reporters of NC surface chemistry. Normal coordinate analysis was used on the metal carbonyl CO stretching vibrations to study the electronic influence of the CdSe NCs on the transition-metal center of the metal carbonyl fragments. These studies demonstrate the utility of organometallic spectroscopic reporters in studying the surface chemistry of NCs.

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Section: ■ Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 98%

Metal-Carbonyl-Functionalized CdSe Nanocrystals: Synthesis, Surface Redox, and Infrared Intensities

2021

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“…www.chemeurj.org of reduced mononuclear transition-metal complexes with CO [34] and CO 2 . [35] More recently, Ca 2 + has been shown to accelerate the rate of O 2 reduction in a Mn system [36] and K + has been shown to facilitate N 2 reduction by low-valent Fe.…”

Section: Resultsmentioning

confidence: 99%

“…Thus, these fluorinated alkoxides support {Cu n O 2 } moieties with both electro-and nucleophilic character. Previously, alkali cations have been reported to increase the reactivity www.chemeurj.org of reduced mononuclear transition-metal complexes with CO [34] and CO 2 . [35] More recently, Ca 2 + has been shown to accelerate the rate of O 2 reduction in a Mn system [36] and K + has been shown to facilitate N 2 reduction by low-valent Fe.…”

Section: Resultsmentioning

confidence: 99%

K⋅⋅⋅F/O Interactions Bridge Copper(I) Fluorinated Alkoxide Complexes and Facilitate Dioxygen Activation

Lum

Tahsini

Golen

et al. 2013

Chemistry A European J

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Seven E[Cu(OR)2] copper(I) complexes (E = K(+), {K(18C6)}(+) (18C6 = [18]crown-6), or Ph4P(+); R = C4F9, CPhMe(F)2, and CMeMe(F)2) have been prepared and their reactivity with O2 studied. The K[Cu(OR)2] species react with O2 in a copper-concentration-dependent manner such that 2:1 and 3:1 Cu/O2 adducts are observed manometrically at -78 °C. Analogous reactivity with O2 is not observed with the {K(18C6)}(+) or Ph4P(+) derivatives. Solution conductivity data demonstrate that these K[Cu(OR)2] complexes do not behave as 1:1 electrolytes in solution. The K(+) ions induce aggregation of multiple [Cu(OR)2](-) units through K⋅⋅⋅F/O interactions and thereby effect irreversible O2 reduction by multiple Cu centers. Bond valence analyses for the potassium cations confirm the dominance of the fluorine interactions in the coordination spheres of K(+) ions. Intramolecular hydroxylation of ligand aryl and alkyl C-H bonds is observed. Nucleophilic reactivity with CO2 is observed for the oxygenated Cu complexes and a Cu(II) carbonate has been isolated and characterized.

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“…Solvents were distilled from the filtrate, under vacuum, and then 6 mL of CH2C12 was added to the crude product. Absolute ethanol, 15 mL, was slowly added to the stirred solution at -78 °C to precipitate yellow [(Ph3P)2N]2[H2Ru4(CO)12] which was filtered, washed consecutively with cold ethanol and pentane, and then dried under vacuum overnight; yield 0.55 g, 76%. Anal.…”

Section: H4ru4(co)12 + 2khmentioning

confidence: 99%

Stepwise deprotonation of H4Ru4(CO)12: high-yield synthesis and carbon-13 NMR spectra of H3Ru4(CO)12- and H2Ru4(CO)122-

Inkrott¹,

Shore²

1979

Inorg. Chem.

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A stepwise, systematic procedure is described for the deprotonation of H4Ru4(CO)12 when it is treated with KH in THF. Reaction with 1 equiv of KH yields the previously reported H3Ru4(CO)12~ion; reaction with 2 equiv of KH yields the new anion H2Ru4(CO)122"; and reaction with 3 equiv of KH yields an equimolar mixture of H2Ru4(CO)122" and Ru4(CO)124'. In this last reaction, the HRu4(CO)123" ion is believed to form initially and then decompose to the products which were isolated. Carbon-13 NMR spectra and infrared spectra of the H2Ru4(CO)i22" ion indicate the presence of carbonyl bridging. The carbon-13 NMR spectrum under conditions of slow exchange (-80 °C) indicates that this dianion is of Cs point symmetry. From infrared and carbon-13 NMR spectra of the potassium and (PPh3)2N+ salts of H2Ru4(CO)122~significant ion pairing is suggested in THF solutions of the potassium salt.

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Infrared, conductance, and kinetic evidence for alkali metal ion interactions with derivatives of manganese carbonylates

Abstract: IR‐Analysen zeigen Kontakt‐Ionenwechsel‐ wirkung zwischen Na und dem Sauerstoff einer äquatorialen CO‐Gruppe in den Verbindungen (I).

Cited by 73 publications

References 6 publications

Metal-Carbonyl-Functionalized CdSe Nanocrystals: Synthesis, Surface Redox, and Infrared Intensities

Metal-Carbonyl-Functionalized CdSe Nanocrystals: Synthesis, Surface Redox, and Infrared Intensities

K⋅⋅⋅F/O Interactions Bridge Copper(I) Fluorinated Alkoxide Complexes and Facilitate Dioxygen Activation

Stepwise deprotonation of H4Ru4(CO)12: high-yield synthesis and carbon-13 NMR spectra of H3Ru4(CO)12- and H2Ru4(CO)122-

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