Nature of bis(2,2'-bipyridine)rhodium(I) in aqueous solutions

Chou, Mei H.; Creutz, Carol; Mahajan, Devinder; Sutin, Norman; Zipp, Arden P.

doi:10.1021/ic00141a023

Cited by 51 publications

(39 citation statements)

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“…HCO 2 H (aq) CO 2(g) + 2H + (aq) + 2e --5.0 kcal/mol H -(aq) + CO 2(g) 24.1 kcal/mol (13) The value for eqn 13 can be used in combination with the analogous hydricities of metalhydrides (eqn 7) to determine if a hydride transfer from the metal-hydride to CO 2 is favorable. For metal-hydrides with hydricities less than 24.1 kcal/mol, as defined by eqn 13, hydride transfer from the metal-hydride to CO 2 will be favorable.…”

Section: Recommendationsmentioning

confidence: 99%

“…5,[9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] While the thermodynamic constants for H 2 in some organic solvents (such as those in dimethylsulfoxide and acetonitrile) 5 have been used with reasonable consistency, a common set of values for the analogous thermodynamic constants in water has not yet been adopted. 5,[9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] While the thermodynamic constants for H 2 in some organic solvents (such as those in dimethylsulfoxide and acetonitrile) 5 have been used with reasonable consistency, a common set of values for the analogous thermodynamic constants in water has not yet been adopted.…”

Section: Introductionmentioning

confidence: 99%

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Predicting the reactivity of hydride donors in water: thermodynamic constants for hydrogen

2015

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The chemical reactivity of hydride complexes can be predicted using bond strengths for homolytic and heterolytic cleavage of bonds to hydrogen. To determine these bond strengths, thermodynamic constants describing the stability of H(+), H˙, H(-), and H2 are essential and need to be used uniformly to enable the prediction of reactivity and equilibria. Due to discrepancies in the literature for the constants used in water, we propose the use of a set of self-consistent constants with convenient standard states.

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Section: Recommendationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Predicting the reactivity of hydride donors in water: thermodynamic constants for hydrogen

2015

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“…1% of the rhodium complex are adsorbed to the TiOz particles. Irradiation of a Rh(bipy)]+/Ti02 suspension of the same composition with the sun lamp for 6 min results in the appearance of the intensive purple colour characteristic for Rh(bipy); (Chou et al, 1982). The latter is entirely associated with the Ti02 particles and remains adsorbed on the powder after centrifugation.…”

Section: Sun Lamp Irradiation Ofmentioning

confidence: 99%

Photoreduction of Nad to Nadh in Semiconductor Dispersions

Cuendet

Grätzel

1984

Photochem & Photobiology

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Band gap illumination of Ti02 (anatase) dispersions in weakly alkaline solutions of nicotinamide-adenine-dinucleotide(NAD+) leads in the presence of rhodium trisbipyridyl complex [ Rh( bipy):*], to continuous generation of biologically active cofactor NADH. Effects of pH, NAD+ and Rh(bipy):+ concentration on the efficiency of this photoconversion process are investigated. The reaction proceeds already in aqueous solution in the absence of externalelectron donors but it is enhanced significantly in the presence of 10% methanol.

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“…Received: October 16,1997 Final version: February 4, 1998 Non-Silica-Based Mesostructured Materials: Hexagonally Mesostructured Array of Surfactant Micelles and 11-Tungstophosphoric Heteropoly Anions** By Akira Taguchi, Takayuki Abe, and Masakazu Iwamoto* Heteropoly tungstates, in particular Keggin ions, are of importance as key compounds for catalysis. [1,2] Although they have mainly been used as a solid or in an aqueous solution so far, if mesostructured materials with Keggin ion frameworks could be synthesized they would be expected to show novel functions in fields such as catalysis, electrochemistry, and host±guest chemistry.…”

Section: Methodsmentioning

confidence: 99%

“…The purple color that developed in the catholyte indicated the formation of the air-sensitive intermediate [Rh I (L 1 ) 2 ] + . [16] Under these conditions, acetophenone (1 mmol) was hydrogenated with a good current efficiency (88 %; charge consumed: 144 C), and (S)-1-phenylethanol was formed with a 66 % yield, and a much lower turnover (9) than on the modified cathode (see Table 1). It is noteworthy that homogeneous electrocatalysis proceeded with the same stereoselectivity (12 %) as polymer- 1-naphthol and 1-indanol)).…”

Section: +mentioning

confidence: 99%

A Chiral Poly(2,2′-bipyridyl rhodium(III) complex) Film Electrode for Asymmetric Induction in Electrosynthesis

Moutet¹,

Duboc-Toia

Ménage

et al. 1998

Adv. Mater.

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Some methods for electrochemical asymmetric induction have been reported in the past. [1] Different types of systems have given noticeable results: chiral supporting electrolytes [2] and solvents, [3] (adsorbed-) surface active chiral auxiliaries, [4] recycling of a homogeneous chiral catalyst, [5] redox catalysis together with a chiral reagent, [6] and chiral chemically modified electrodes. [7] The latter approach seems to be excellent, because asymmetric induction can be achieved using extremely small amounts of the inducing reagent, permanently immobilized at an electrode surface. This approach has been used for the synthesis of chiral electrode/electrolyte interfaces, which have afterwards been applied in electrosynthesis. Up to now, the reduction of prochiral carbonyl compounds on graphite functionalized with amino acids, [7] the selective reduction of pnitrophenol on carbon electrodes modified with a-cyclodextrin, [8] the reduction of prochiral olefins on poly-L-valine-coated graphite, [9] the oxidation of unsymmetric sulfides on poly(amino acid) film electrodes, [10] or the oxi-dation of racemic Co(phen) 3 2+ (phen = 1,10-phenanthroline) on a D-Ru(phen) 3 2+ -montmorillonite clay film to produce L-Co(phen) 3 2+ in enantiomeric excess, [11] are some striking examples of asymmetric electrosyntheses on chemically modified electrodes. Surprisingly, transition-metal catalysts able to combine high activity and selectivity have never been used for this purpose. Asymmetric induction in electrosynthesis may be expanded by the use of molecular electrodes based on transition-metal complexes with chiral ligands. We report here the first example of enantioselective electrocatalytic hydrogenation of prochiral ketones on a carbon electrode modified by a rhodium(III) complex catalyst with chiral bipyridyl ligands. Recently, we have demonstrated that electropolymerization of [Rh III (L) 2 Cl 2 ] + complexes [12] (L = pyrrole-substituted 2,2¢-bipyridine and 1,10-phenanthroline) on carbon surfaces is an effective technique for the synthesis of active electrode materials for the electrocatalytic hydrogenation of organic compounds in aqueous electrolytes. [12a,13] A rhodium hydride complex formed from the electrochemically reduced Rh I complex was assumed [13] to be the key intermediate (Scheme 1). Thus, this electrocatalytic system can be seen as electrochemically promoted transfer hydrogenation using water as the hydrogen donor, instead of a secondary alcohol or an organic acid like in regular catalytic transfer hydrogenation. Using the same strategy, we have carried out the enantioselective hydrogenation of prochiral aromatic ketones on carbon felt electrodes modified by oxidative electropolymerization of the [Rh(L 2 ) 2 Cl 2 ] + complex. Results have been compared with those obtained in homogeneous experiments carried out using the [Rh(L 1 ) 2 Cl 2 ] + complex. The ligands L 1 and L 2 used in this study are shown in Figure 1.[**] The authors thank the CNRS for financial support. Dr. A. Deronzier is warmly acknowledged f...

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Nature of bis(2,2'-bipyridine)rhodium(I) in aqueous solutions

Cited by 51 publications

References 0 publications

Predicting the reactivity of hydride donors in water: thermodynamic constants for hydrogen

Predicting the reactivity of hydride donors in water: thermodynamic constants for hydrogen

Photoreduction of Nad to Nadh in Semiconductor Dispersions

A Chiral Poly(2,2′-bipyridyl rhodium(III) complex) Film Electrode for Asymmetric Induction in Electrosynthesis

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