Introduction to Organic Electrochemistry

Rifi, M. R.; Covitz, Frank.; Stocker, Jack H.

doi:10.1149/1.2134033

Cited by 31 publications

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“…-= -1.67 V vs. NHE), and CH3C1 (PI-= -2.23 V vs. NHE) (26). In these cases, the photoinduced electron transfer mechanism from the ~~( d~~m )~~0 cluster in their lowest energy 3~2 states to the chlorocarbon molecules is clearly thermodynamically unfavorable.…”

Section: Thermodynamics the Emission Spectra Of The ~~( D~~m )~~0~mentioning

confidence: 97%

Photoinduced oxidative degradation of unsaturated M₃(dppm)₃CO²⁺ clusters (M = Pd, Pt) by chlorocarbons and chloride ion

Harvey¹,

Provencher²,

Gagnon³

et al. 1996

Can. J. Chem.

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Both ~, ( d~~r n ) ,~O~+ clusters (M = Pd, Pt) photoreact with chlorocarbons (Cl-R; R = CCl,, CHCl,, CH2C1, C6H5, ClOHl5 (adamant~l)) and chloride ion (slowly) to produce the oxidized mononuclear species M(dppm)Cl, as a sole isolated Mcoordinated inorganic product. Such reactions do not proceed in the dark, except for R = CH2C6H5. Among the organic products, the coupling compound R-R (R = C6H5) is observed along with many phosphine compounds such as P(C6H5),. In an attempt to elucidate the photoinduced mechanism at the early stage of the phototransformations, the following have been investigated : the ground state binding constants (K,, for M = Pd in methanol), the photochemical quantum yields of cluster disappearance (Qdis for M = Pd) as a function of substrates, substrate concentrations, excitation wavelengths, solvents (ethanol vs toluene), and presence of CO, and the emission lifetimes (7, for M = Pt) at 77 K as a function of substrate concentrations (CH,Cl, and CHCI,) in ethanol and toluene. Some of the experimental conclusions have also been corroborated theoretically using density functional theory. Geometry optimization calculations have been performed for the model compounds P~,(PH,)~co~+-.c~-, Pd3(PH3)62+, P~, ( P H , )~C~~+ . C~~, P~,(PH,)~CO~+~-CI-CH,, and P~,(PH,)~co~+ in their ground states.Key words: atom abstraction, photochemistry, C-C1 bond, clusters, host-guest.RCsumC : Les agrCgats ~, ( d~~r n ) ,~0~+ (M = Pd, Pt) photorkagissent tous les deux avec les chlorocarbones (Cl-R; CCI,, CHCl,, CH2C1, C6H5, ClOHl6 (adamantyle)) et avec l'ion chlorure (lentement) pour conduire B des espkces mononuclCaires oxydCes M(dppm)Cl, qui correspondent au seul produit inorganique M-coordinC B Ctre isole. Ces reactions ne se produisent pas B la noirceur, except6 pour le composC R = CH2C6H5. Parmi les composCs organiques, on observe le composC de couplage R-R (R = C6H5) ainsi que plusieurs phosphines telle que la P(C6H5),. Dans le but d'Clucider le mCcanisme photoinduit dans 1'Ctape initiale des phototransfonnations, on a examink les caractCristiques suivantes : les constantes d'association dans 1'Ctat fondamental (K,,, pour M = Pd dans le methanol), les rendements quantiques photochimiques pour la disparition des agrCgats (Qdis pour M = Pd) en fonction des substrats, des concentrations de substrat, des longueurs d'onde d'excitation, des solvants (Cthanol vs. tolukne) et de la presence de CO et les durCes de vie d'Cmissions (7, pour M = Pt), B 77 K, en fonction des concentrations de substrat (

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Section: Thermodynamics the Emission Spectra Of The ~~( D~~m )~~0~mentioning

confidence: 97%

Photoinduced oxidative degradation of unsaturated M₃(dppm)₃CO²⁺ clusters (M = Pd, Pt) by chlorocarbons and chloride ion

Harvey¹,

Provencher²,

Gagnon³

et al. 1996

Can. J. Chem.

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“…The energy to overcome the reaction barrier is introduced by electrical energy, which can be finely tuned, instead of thermal energy and thus can be applied at low temperatures to thermally-sensitive compounds 739) . The processes offer great ease in monitoring the reactions and are suitable for continuous and automatic operation 743) . Spontaneous electrochemical reactions which produce chemicals and electric energy simultaneously, e.g.…”

Section: Disappointments and Advantagesmentioning

confidence: 99%

Non-aqueous electrolyte solutions in chemistry and modern technology

Barthel

Gores

Schmeer

et al. 1983

Topics in Current Chemistry

114

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“…Under the influence of the Passage ciency have been discovered (1)(2)(3)(4). provided that of an electric current, the contents of the calorimeter there are no unwanted side reactions accompanying change from a defined initial state to a defined final the reaction of interest, it would seem that the obser-State, a t constant pressure and (in our d i~h e n~l -vation of reactions taking place inside a calori-ether calorimeter, see Experimental section below) meter could, in principle at least, lead to valuable constant temperature.…”

Section: Introductionmentioning

confidence: 99%

Calorimetric study of an electrochemical reduction

Turner¹,

Pritchard²

1978

Can. J. Chem.

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Introduction to Organic Electrochemistry

Abstract: not Available.

Cited by 31 publications

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Photoinduced oxidative degradation of unsaturated M₃(dppm)₃CO²⁺ clusters (M = Pd, Pt) by chlorocarbons and chloride ion

Photoinduced oxidative degradation of unsaturated M₃(dppm)₃CO²⁺ clusters (M = Pd, Pt) by chlorocarbons and chloride ion

Non-aqueous electrolyte solutions in chemistry and modern technology

Calorimetric study of an electrochemical reduction

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Introduction to Organic Electrochemistry

Abstract: not Available.

Cited by 31 publications

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Photoinduced oxidative degradation of unsaturated M3(dppm)3CO2+ clusters (M = Pd, Pt) by chlorocarbons and chloride ion

Photoinduced oxidative degradation of unsaturated M3(dppm)3CO2+ clusters (M = Pd, Pt) by chlorocarbons and chloride ion

Non-aqueous electrolyte solutions in chemistry and modern technology

Calorimetric study of an electrochemical reduction

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Photoinduced oxidative degradation of unsaturated M₃(dppm)₃CO²⁺ clusters (M = Pd, Pt) by chlorocarbons and chloride ion

Photoinduced oxidative degradation of unsaturated M₃(dppm)₃CO²⁺ clusters (M = Pd, Pt) by chlorocarbons and chloride ion