Matrix Isolation Infrared and Theoretical Study of the Reaction of VCl4 with NH3 and (CH3)3N

Kayser, David A.; Ault, Bruce S.

doi:10.1021/jp0491459

Cited by 4 publications

(2 citation statements)

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“…Instead, several new vibrations appeared in the Raman spectrum in the wavenumber region of ñ = 2300-2600 cm À1 , and these may be ascribed to NÀD stretching modes originating from the various deuterated ammonia forms (ND 3 3 ] À ), consistent with hydrogen-deuterium exchange. [17] A dehydrogenation profile of the [CaAB+2 ND 3 ] sample is shown in Figure 3. The signals at m/z = 17, 18, 19, and 20, which correspond to NDH + (or NH 3 + ), NDH 2 + , ND 2 H + , and ND 3 + , were detected at temperatures < 100 8C.…”

Section: Dehydrogenation Mechanism Of Calcium Amidoborane Ammoniatementioning

confidence: 99%

Mechanistic Investigation on the Formation and Dehydrogenation of Calcium Amidoborane Ammoniate

Chua¹,

Wen²,

Shaw³

et al. 2012

ChemSusChem

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Possessing high H2 capacities and interesting dehydrogenation behavior, metal amidoborane ammoniates were prepared by reacting Ca(NH2)2, MgNH, and LiNH2 with ammonia borane to form Ca(NH2BH3)2⋅2 NH3, Mg(NH2BH3)2⋅NH3, and Li(NH2BH3)2⋅NH3 (LiAB⋅NH3). Insight into the mechanisms of amidoborane ammoniate formation and dehydrogenation was obtained by using isotopic labeling techniques. Selective 15N and 2H labeling showed that the formation of the ammoniate occurs via the transfer of one H(N) from ammonia borane to the [NH2]− unit in Ca(NH2)2 giving rise to NH3 and [NH2BH3]−. Supported by theoretical calculations, it is suggested that the improved dehydrogenation properties of metal amidoborane ammoniates compared to metal amidoboranes are a result of the participation of a strong dihydrogen bond between the NH3 molecule and [NH2BH3]−. Our study elucidates the reaction pathway involved in the synthesis and dehydrogenation of Ca(NH2BH3)2⋅2 NH3, and clarifies our understanding of the role of NH3, that is, it is not only involved in stabilizing the structure, but also in improving the dehydrogenation properties of metal amidoboranes.

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Section: Dehydrogenation Mechanism Of Calcium Amidoborane Ammoniatementioning

confidence: 99%

Mechanistic Investigation on the Formation and Dehydrogenation of Calcium Amidoborane Ammoniate

Chua¹,

Wen²,

Shaw³

et al. 2012

ChemSusChem

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“…With NH 3 a 1:1 complex Cl 4 V Á NH 3 is formed and in this case irradiation causes HCl elimination to give Cl 3 VNH 2 and HCl. 284 Similarly the 1:1 complex formed by VCl 4 and MeOH is destroyed by photolysis, the product being Cl 3 VOMe. 285 As mentioned above CrO 2 Cl 2 often shows similar chemistry to OVCl 3 in these reactions and some studies have focussed upon the chromium species.…”

Section: Groups 4 Tomentioning

confidence: 99%

Chemistry in low-temperature matrices

Almond

Goldberg

2007

Annu. Rep. Prog. Chem., Sect. C: Phys. Chem.

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the Progress of Chemistry, Section C. The report is divided into sections: weak adducts and conformational isomers; reactions of atoms; high-temperature molecules; photochemistry; biological molecules; astrochemistry. The last two sections reflect the fact that matrix isolation now extends into areas outside the traditional mainstream disciplines of chemistry. There are a number of areas where substantial progress has been made during the period of this report. First, the routine use of laser-ablation to generate atoms and to initiate atomic reactions in matrices has increased the scope of matrix isolation to synthesise many new molecular species in inorganic chemistry. Laser-ablation allows ground state atoms to be more easily studied than is the case when atoms are produced by thermal methods. Moreover, this procedure allows atoms to be generated from materials where thermal production is difficult. Secondly, the manufacture of more efficient closed-cycle helium refrigerators allows hydrogen matrices to be deposited readily. A significant body of work therefore has focussed upon metal hydrides, dihydrogen complexes and other hydrogen species in matrices. Underpinning all of this experimental work are theoretical calculations, without which the correct identification of most matrix isolation molecules would remain dangerously ambiguous. Infrared spectroscopy remains-as it has for the past 50 years-the workhorse of matrix isolation studies. It does seem that this situation will not change-it is impossible to conceive of another spectroscopic method that combines the necessary sensitivity to study molecules at very low dilution with the structural information required to make a reasonably certain identification.

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Matrix Isolation Spectroscopic Studies: Thermal and Soft Photochemical Bimolecular Reactions

Ault

2018

Frontiers and Advances in Molecular Spectroscopy

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Matrix Isolation Infrared and Theoretical Study of the Reaction of VCl₄ with NH₃ and (CH₃)₃N

Cited by 4 publications

References 22 publications

Mechanistic Investigation on the Formation and Dehydrogenation of Calcium Amidoborane Ammoniate

Mechanistic Investigation on the Formation and Dehydrogenation of Calcium Amidoborane Ammoniate

Chemistry in low-temperature matrices

Matrix Isolation Spectroscopic Studies: Thermal and Soft Photochemical Bimolecular Reactions

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