Studies on the mechanism of transition-metal-assisted sodium borohydride and lithium aluminum hydride reductions

Osby, John O.; Heinzman, Stephen W.; Ganem, Bruce

doi:10.1021/ja00261a011

Cited by 111 publications

(49 citation statements)

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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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“…20 We propose that a transition metal-assisted borohydride reduction of the nitrile to an amine with the product adsorbing to the colloid surface adequately accounts for the observed spectra. 21 The reaction is depicted as follows :…”

Section: Resultsmentioning

confidence: 99%

Surface-enhanced Raman spectra of the reduction product of 4-cyanopyridine on copper colloids

Coyle

Chumanov

Jagodzinski

1998

J. Raman Spectrosc.

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“…It is relatively stable in aqueous solutions but is hydrolysed at lower pH according to Equation (1). [1] This is an acid-catalysed reaction, and the intermediate BH 3 …”

Section: Introductionmentioning

confidence: 99%

“…This is an acid-catalysed reaction, and the intermediate BH 3 H 2 O or BH 3 OH -is formed en route to borate (BO 2 -/H 3 BO 3 ). The decrease in the initial rate of hydrogen evolution is due to the increasing pH of the solution, which in turn results in the formation of the metaborate ion according to Equation (2).…”

Section: Introductionmentioning

confidence: 99%

BH₄^–‐Promoted, Radical‐Initiated, Catalytic Oxidation of (CH₃)₂SO by N₂O in Aqueous Solution

Yanus

Yardeni²,

Maimon

et al. 2016

Eur J Inorg Chem

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Studies on the mechanism of transition-metal-assisted sodium borohydride and lithium aluminum hydride reductions

Cited by 111 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

Surface-enhanced Raman spectra of the reduction product of 4-cyanopyridine on copper colloids

BH₄^–‐Promoted, Radical‐Initiated, Catalytic Oxidation of (CH₃)₂SO by N₂O in Aqueous Solution

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Studies on the mechanism of transition-metal-assisted sodium borohydride and lithium aluminum hydride reductions

Cited by 111 publications

References 0 publications

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

Surface-enhanced Raman spectra of the reduction product of 4-cyanopyridine on copper colloids

BH4–‐Promoted, Radical‐Initiated, Catalytic Oxidation of (CH3)2SO by N2O in Aqueous Solution

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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

BH₄^–‐Promoted, Radical‐Initiated, Catalytic Oxidation of (CH₃)₂SO by N₂O in Aqueous Solution