Mechanism of sodium borohydride-cobaltous chloride reductions

Heinzman, Stephen W.; Ganem, Bruce

doi:10.1021/ja00388a063

Cited by 133 publications

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“…Noteworthy is also the possibility of using transition elements, such as Co(II), Ni(II) [25], and Rh(III) [26], to modify the reducing power of the tetrahydroborate. For example, [BH 4 ] − cannot reduce nitriles, amides, and olefins, but it can do so in combination with transition element halides [27,28]. Recent observations of the effects of Au(III), Pd(II), and Pt(II) on generation of arsane [13] confirm a peculiar chemistry in this system, and in this study we report a similar behaviour with Rh (III).…”

Section: Mechanistic Interference From Rhodium(iii)supporting

confidence: 79%

The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BH_nD_4-n]⁻ and the Effect of Trace Amounts of Rh(Iii) Ions

D’Ulivo

Mester

Sturgeon

et al. 2012

J. Am. Soc. Mass Spectrom.

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Recent studies of the formation of arsane in the borohydride/arsenate reaction demonstrate the occurrence of condensation cascades whereby small quantities of di-and triarsanes are formed. In this study, the isotopic composition of these di-and triarsanes was examined using deuterium labelled borohydrides. A statistical model was employed to construct the mass spectra of all diarsane and triarsane isotopologues (As 2 H n D 4-n and As 3 H n D 5-n ) from the mass spectra of isotopically pure compounds (As 2 H 4 , As 2 D 4 , As 3 H 5 , and As 3 D 5 ). Subsequent deconvolution of the experimental mixed spectra shows that incorporation of hydrogen closely follows the binomial distribution, in accord with arsane formation. The H/D distribution in arsane, diarsane, and triarsane isotopologues is binomial in the absence of any interference. However, this is significantly altered by the presence of some transition metals; presented here, for the first time, are the effects of Rh(III). The presence of Rh(III) in the As(III)/ [BD 4 ] − system entails the incorporation of hydrogen into the arsanes arising from the solvent, altering the expected binomial H/D distribution.

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Section: Mechanistic Interference From Rhodium(iii)supporting

confidence: 79%

The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BH_nD_4-n]⁻ and the Effect of Trace Amounts of Rh(Iii) Ions

D’Ulivo

Mester

Sturgeon

et al. 2012

J. Am. Soc. Mass Spectrom.

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“…Galactose is a relatively mild reducing agent used for the reduction of silver ions in the presence of CTAB as stabilizer. The use of stabilizers such as surfactants and polymers is highly important to obtain stable monodisperse nanoparticles [22]. Micelles increase the rate of bimolecular reactions by concentrating both the reactants at their surfaces.…”

Section: Resultsmentioning

confidence: 99%

Mechanistic and kinetic study of the formation of silver nanoparticles by reduction of silver(I) in the presence of surfactants and macromolecules

Ismail

Ewais

2015

Transition Met Chem

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The kinetics of formation of silver nanoparticles by reduction of silver(I) with galactose were studied spectrophotometrically in the presence of surfactants and chitosan as stabilizing agents. The reaction was carried out under pseudo-first-order conditions by using a tenfold excess of [galactose] over [Ag ? ]. The effects of cetyltrimethylammonium bromide (cationic surfactant) and sodium dodecyl sulfate (anionic surfactant) on the reaction rate have been studied. Chitosan inhibits the rate of reaction by up to 70 %. TEM imaging shows that there is no aggregation of silver nanoparticles in the presence of chitosan. The rate of reaction increases with increasing [OH -]. A mechanism for the reaction is proposed, and the rate equation derived from this mechanism was consistent with the experimental behaviors. Thermodynamic activation parameters were calculated.

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“…In another example of a metal chloride assisted reduction, nitrile 89 is reduced with sodium borohydride-cobalt(II) chloride hexahydrate to give the primary amine 90 in high yield; [149] the formation of secondary amines as potential byproducts is not observed. [160,161] Scheme 25 Reduction of Nitriles with Sodium Borohydride and Transition Metal Salts [150,160] The combined use of diisobutylaluminum hydride and sodium borohydride represents a further effective method for reducing nitriles to primary amines. Nitriles rapidly consume 1 equivalent of hydride from the diisobutylaluminum hydride reagent, but further hydride uptake is very sluggish.…”

Section: Scheme 19 Synthesis Of A-substituted Primary Amines By Additmentioning

confidence: 99%

Synthesis by Reduction

Enders¹,

Schaumann²

2009

Category 5, Compounds With One Saturated Carbon Heteroatom Bond

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Mechanism of sodium borohydride-cobaltous chloride reductions

Cited by 133 publications

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The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BH_nD_4-n]⁻ and the Effect of Trace Amounts of Rh(Iii) Ions

The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BH_nD_4-n]⁻ and the Effect of Trace Amounts of Rh(Iii) Ions

Mechanistic and kinetic study of the formation of silver nanoparticles by reduction of silver(I) in the presence of surfactants and macromolecules

Synthesis by Reduction

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Mechanism of sodium borohydride-cobaltous chloride reductions

Cited by 133 publications

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The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BHnD4-n]− and the Effect of Trace Amounts of Rh(Iii) Ions

The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BHnD4-n]− and the Effect of Trace Amounts of Rh(Iii) Ions

Mechanistic and kinetic study of the formation of silver nanoparticles by reduction of silver(I) in the presence of surfactants and macromolecules

Synthesis by Reduction

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The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BH_nD_4-n]⁻ and the Effect of Trace Amounts of Rh(Iii) Ions

The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BH_nD_4-n]⁻ and the Effect of Trace Amounts of Rh(Iii) Ions