12184-84-8

Basic information

• Product Name: deuteriodeuterium(1+)
• Synonyms: dideuterium(.1+)
• CAS NO: 12184-84-8
• Molecular Formula: D₂
• Molecular Weight: 4.028202
• Mol File: 12184-84-8.mol
• Article Data: 157

Chemical Properties

• CAS DataBase Reference: deuteriodeuterium(1+)(CAS DataBase Reference)
• NIST Chemistry Reference: deuteriodeuterium(1+)(12184-84-8)
• EPA Substance Registry System: deuteriodeuterium(1+)(12184-84-8)

Safety Data

• Hazardous Substances Data: 12184-84-8(Hazardous Substances Data)

Upstream product

• 7732-18-5 water 
• 558-20-3 methane 
• 7789-20-0 water-d2 
• 7440-23-5 sodium 
• 13537-07-0 silane-d4 
• 7440-21-3 monosilane 
• 17030-72-7 trideuteriomethylium 
• 60094-88-4 CH₂⁽²⁾H⁽¹⁺⁾ 
• 58576-33-3 CH⁽²⁾H₂⁽¹⁺⁾ 
• 1076-43-3 benzene-d6 
• 1333-74-0 hydrogen 
• 13762-18-0 half-deuterated hydrogen sulphide 
• 7783-06-4 hydrogen sulfide 
• 13536-94-2 deuterium sulfide 

Downstream Products

• 16873-17-9 deuterium D2, ortho 
• 13536-94-2 deuterium sulfide 
• 14464-47-2 deuterium 
• 12144-04-6 carbon monoxide⁽¹⁺⁾ 
• 676-55-1 methane-d2 
• 676-49-3 Monodeuteromethan 
• 14674-67-0 water 
• 127972-68-3 (⁽²⁾H)3Ru₃(CC⁽²⁾HC₆H₅CH⁽²⁾HC₆H₅)(CO)9 
• 113088-98-5 trans-(Os(η2-HD)(D)((C2H5)2PCH2CH2PPh2)2)BF4 
• 20396-66-1 diborane-d6 
• 14885-60-0 tritium 
• 14885-60-0 deuterium-tritium-hydrogen 

Relevant articles and documents

Protonation studies of the new iron carbonyl cyanide trans-[Fe(CO) 3(CN)2]2-: Implications with respect to hydrogenases

The new iron carbonyl cyanide trans-[Fe(CN)2(CO) 3]2-, [2]2-, forms in high yield via photosubstitution of Fe(CO)5 with 2 equiv of Et4NCN. Protonation of [2]2- generated [HFe(CN)

The decomposition pathways for LiBD4-MgD2 multicomponent systems investigated by in situ neutron diffraction

Complex hydride-binary hydride multicomponent hydrogen storage systems offer great potential for practical hydrogen stores because their dehydrogenation thermodynamics can be tailored through a destabilisation mechanism whilst maintaining a high hydrogen

Visible-light-driven hydrogen evolution from water using a noble-metal-free polyoxometalate catalyst

In an effort to address the need to develop hydrolytically more stable, molecular water reduction catalysts (WRCs) amenable to in-depth investigation, we report here one prototype: a tetra-manganese-containing V-centered polyoxotungstate, Na10[Mn4(H2O) 2(VW9O34)2] (1). The electronic structure of 1 was elucidated using the DFT approach. Complex 1 is readily prepared by a one-pot procedure in aqueous solution and catalyzes the reduction of water using visible light irradiation (λ = 455 nm) with [Ru(bpy) 3]2+ and triethanolamine (TEOA) as a photosensitizer and sacrificial electron donor, respectively. Upon irradiation, the excited state [Ru(bpy)3]2+* is oxidatively quenched by 1, as confirmed by steady-state and time-resolved fluorescence decay studies, to form [Ru(bpy)3]3+ and a reduced form of the catalyst. The [Ru(bpy)3]2+ is rapidly regenerated by reaction with TEOA. The reduced form of the catalyst, 1, reacts with water to generate hydrogen. Isotope labeling experiments demonstrate that the hydrogen comes from water. The stability of the catalyst was assessed using different spectroscopic methods. A mechanism based on experimental results is proposed.

Design considerations for chiral frustrated Lewis pairs: B/N FLPs derived from 3,5-bicyclic aryl piperidines

Herein, 3,5-bicyclic aryl piperidines are derivatized to generate chiral B/N FLPs. Initially, the twofold symmetric amine C6H2F2(C5H8NiPr) 1 was converted in a series of synthetic steps to the styrene-derivative C6HF2(C5H8NiPr)(CH═CH2) 4. Efforts to hydroborate the vinyl fragment proved challenging as a result of the strongly basic nitrogen, although the species C6HF2(C5H8N(H)iPr)(CH2CH2B(OH)(C6F5)2) 5 was crystallographically characterized. Modification of the system was achieved by conversion of the amine C6H2F2(C5H8NH) 6 to C6HF2(C5H8NPh)(CH═CH2) 9. Hydroboration of 9 with 9-BBN or HB(C6F5)2 gave C6HF2(C5H8NPh)(CH2CH2BBN) 10 or C6HF2(C5H8NPh)(CH2CH2B(C6F5)2) 11, respectively. The latter species was derivatized by complexation of PPh3 to give C6HF2(C5H8NPh)(CH2CH2B(C6F5)2)(PPh3) 12. The Lewis acidities of 10 and 11 were assessed by the Gutman-Beckett test and by computations of the FIA and GEI. While 10 did not effect HD scrambling or hydrogenation of N-phenylbenzylimine, 11 was effective in HD scrambling. Despite this, no reduction of N-t-butylbenzylimine or N-phenylbenzylimine was achieved. These data demonstrate that 10 lacks the threshold combination of Lewis acidity and basicity to activate H2, while 11 lacks the steric demands about boron to preclude classical Lewis acid-base bond formation with imine substrates.

A structural effect in direct reactions: Kinetics of D abstraction from Pt(110) 1×2 surfaces with gaseous H atoms

Deuterium-covered Pt(110) surfaces were subjected to a flux of thermal H atoms at 100 K. The rates of product formation, HD and D2, were measured simultaneously with H atom exposure as a function of D coverage. D2 as a product and the kinetics of HD formation contradict the operation of Eley-Rideal type mechanisms in these reactions. More appropriate seems the assumption that a hot-atom type mechanism operates in abstraction of adsorbed D by gaseous H. The H/D abstraction kinetics at Pt(110) surfaces are completely different from that observed previously at Pt(111) surfaces. This structural effect puts a further question mark on the validity of the Eley-Rideal mechanisms in abstraction reactions and is interpreted in the present work as a consequence of the interrelation between a hot-atom mechanism and the surface structure of the reconstructed substrate.

Gas-phase chemistry of bare transition-metal ions in comparison

Some basic principles of gas-phase organometallic chemistry are demonstrated, exemplified for the model compound 2-methylbutanenitrile (5). The reactions of first-row transition-metal ions with 5 and its deuterated isotopomers 5a-5c reveal a distinct infl

Combinatorial Identification of Hydrides in a Ligated Ag40 Nanocluster with Noncompact Metal Core

No formation of bulk silver hydride has been reported. Until very recently, only a few silver nanoclusters containing hydrides have been successfully prepared. However, due to the lack of effective techniques and also poor stability of hydride-containing Ag nanoclusters, the identification of hydrides' location within Ag nanoclusters is challenging and not yet achieved, although some successes have been reported on clusters of several Ag atoms. In this work, we report a detailed structural and spectroscopic characterization of the [Ag40(DMBT)24(PPh3)8H12]2+ (Ag40H12) cluster (DMBT = 2,4-dimethylbenzenethiol). The metal framework consists of three concentric shells of Ag8?Ag24?Ag8, which can be described as (ν1-cube)?(truncated-ν3-octahedron)?(ν2-cube), respectively. The presence of 12 hydrides in each cluster was systematically identified by various techniques. Based on a detailed analysis of the structural features and 1H and 2H NMR spectra, the positions of the 12 hydrides were determined to be residing on the 12 edges of the cubic core. As a result, the electron count of the Ag40 cluster is a two-electron superatomic system instead of a 14-electron system. Moreover, based on our DFT calculations and experimental probes, it was demonstrated that the 12 hydrides play a crucial role in stabilizing both the electronic and geometric structure of the Ag40H12 cluster. The successful synthesis of stable hydride-containing Ag nanoclusters and the identification of hydride positions are expected to simulate research attention on both synthesis and application of hydride-containing Ag nanomaterials.

Photolysis of Hydrogen Bromide-Deuterium Bromide Mixtures at 2537 Angstroem

The photochemistry of hydrogen bromide-deuterium bromide mixtures exposed to 2537-Angstroem light was investigated.Results of experiments in which various mixtures of the two bromides were irradiated and then assayed for H2, HD, and D2 are interpreted in

Decomposition of formic acid over silica encapsulated and amine functionalised gold nanoparticles

Formic acid has recently attracted considerable attention as a safe and convenient source of hydrogen for sustainable chemical synthesis and renewable energy storage. Here, we show that silica encapsulated and amine functionalised gold nanoparticles are h

Protonated nitric acid. Structure and relative stability of isomeric H2NO3+ ions in the gas phase

Gaseous H2NO3+ ions have been obtained from direct protonation of nitric acid by H3+, CH5+, and H3O+ as well as from the protonation of C2H5

Unravelling the Mechanism of Basic Aqueous Methanol Dehydrogenation Catalyzed by Ru-PNP Pincer Complexes

Ruthenium PNP complex 1a (RuH(CO)Cl(HN(C2H4Pi-Pr2)2)) represents a state-of-the-art catalyst for low-temperature (2 and CO2. Herein, we describ

Molecular hydrogen formation from photocatalysis of methanol on TiO 2(110)

It is well established that adding methanol to water could significantly enhance H2 production by TiO2. Recently, we have found that methanol can be photocatalytically dissociated on TiO2(110) at 400 nm via a stepwise mechanism. However, how molecular hydrogen can be formed from the photocatalyzed methanol/TiO2(110) surface is still not clear. In this work, we have investigated deuterium formation from photocatalysis of the fully deuterated methanol (CD3OD) on TiO 2(110) at 400 nm using a temperature programmed desorption (TPD) technique. Photocatalytic dissociation products formaldehyde (CD2O) and D-atoms on BBO sites (via D2O TPD product) have been detected. In addition to D2O formation by heating the photocatalyzed methanol/TiO2(110) surface, we have also observed D2 product formation. D2 is clearly formed via thermal recombination of the D-atoms on the BBO sites from photocatalysis of methanol. Experimental results indicate that D2O formation is more important than D 2 formation and that D2 formation is clearly affected by the D2O formation process.

Investigation and enhancement of the stability and performance of water reduction systems based on cyclometalated iridium(III) complexes

Water reduction systems that use a bis-cyclometalated IrIII photosensitiser (PS) along with homogeneous Pd complexes as a source of in-situ-formed colloidal Pd as the water reducing complex (WRC) and triethylamine (TEA) as the sacrificial electron donor were tested and characterised with respect to their photocatalytic H2 production performance. It was confirmed that substitution of the 2-(pyridin-2-yl)benzen-1- ide (pyb) ligand in the well-known system [Ir(pyb)2(bpy)]+ (bpy=2,2′-bipyridine) by the fluorinated cyclometalating ligand 5-fluoro-2-(5-methylpyridin-2-yl)benzen-1-ide (Fmpyb) tremendously enhanced the H2 production rate. Moreover, variation of the bidentate N^N ligand bpy by alkyl substitution in the 4,4′-position resulted in an increase in the H2 production yield by a factor of three. The incident-photon-to-hydrogen-efficiency could be enhanced from 2.6 to 12.3 %. Furthermore, a new dinuclear Co complex was used as a reduction catalyst and showed up to 760 turnovers after 20 h. A detailed study of the concentration impact of all components in the photoredox system was performed. DFT calculations were used to aid the explanation of the findings. Teamwork 2.0: A highly active system for photocatalytic water reduction consisting of an Ir photosensitiser and a Pd dichloro complex as the source of catalytically active Pd0 is described. Additionally, the introduction of a hitherto unknown dinuclear Co complex as a water reduction centre resulted in a system with a comparably high initial activity. Copyright

Visible light-catalytic dehydrogenation of benzylic alcohols to carbonyl compounds by using an eosin y and nickel-thiolate complex dual catalyst system

We developed a simple and environmentally benign visible-light-driven dehydrogenation of benzylic alcohols to the corresponding aldehydes or ketones. By using the dual catalyst system consisting of eosin Y as a photocatalyst and a Ni(ii) complex as a proton reduction catalyst, we could dehydrogenate benzylic alcohols to aldehydes or ketones with excellent yields under mild conditions. The sole byproduct is hydrogen gas.

Light-driven hydrogen generation: Efficient iron-based water reduction catalysts

(figure represented) Let your light shine: A novel state-of-theart system for light-driven proton reduction with iron catalysts was developed (see scheme; SR = sacrificial reagent). It consists of simple iron carbonyl complexes such as [Fe3(CO)

Mechanism of the Catalytic Hydrogen Production by Gold Sols. H/D Isotope Effect Studies

The H/D isotope effect on the catalytic production of the hydrogen from water using either Cr2+ or (CH2)2OH radicals as reductants was studied.The catalysts used were gold sols stabilized by either citrate or poly(vinylsulfate).Similar isoto

A High-Temperature Photochemistry Study of the D + ND3 Reaction

The kinetics of the D + ND3 reaction (2) has been studied from 590 to 1220 K by using the high-temperature photochemistry (HTP) technique.D(12S) atoms were generated by flash photolysis of ND3 and monitored by time-resolved atomic resonance fluorescence with pulse counting. k2(T) is determined to be 3.2 x 1E-10 exp(-8810 K/T) cm3 molecule-1 s-1.Accuracy assessments are discussed in the text.Comparison to k1(T) for H + NH3 (1) measured in the same apparatus and over a similar temperature range shows that k2(T) is smaller. k1(T) and k2(T) agree reasonably well with calculations based on transition-state theory and a simple tunneling model using the same potential energy surface for both reactions.Considered alone, k2(T) can also be modeled without tunneling.

Steam reforming of biomass based oxygenates-Mechanism of acetic acid activation on supported platinum catalysts

The activation of acetic acid during steam reforming reactions over Pt-based catalysts has been probed by decomposing CH3COOD over Pt/C. The product mixture contained CO2, CH4 and its D-analogs (CH4 - x Dx

Molecular hydrogen formation from proximal glycol pairs on TiO 2(110)

Understanding hydrogen formation on TiO2 surfaces is of great importance, as it could provide fundamental insight into water splitting for hydrogen production using solar energy. In this work, hydrogen formation from glycols having different numbers of methyl end-groups has been studied using temperature-programmed desorption on reduced, hydroxylated, and oxidized rutile TiO2(110) surfaces. The results from OD-labeled glycols demonstrate that gas-phase molecular hydrogen originates exclusively from glycol hydroxyl groups. The yield is controlled by a combination of glycol coverage, steric hindrance, TiO2(110) order, and the amount of subsurface charge. Combined, these results show that proximal pairs of hydroxyl-aligned glycol molecules and subsurface charge are required to maximize the yield of this redox reaction. These findings highlight the importance of geometric and electronic effects in hydrogen formation from adsorbates on TiO2(110).

Dihydrogen Evolution by Photolysis of HFe(CO)4(-) and the Photoassisted Water Gas Shift Reaction: a Possible Dinuclear Reductive Elimination Mechanism

The photolysis of HFe(CO)4(-) results in the evolution of a 1:1 mixture of H2 and CO under Ar and assists the water gas shift reaction under 1 atm pressure of CO; a suggested mechanism involves the dinuclear reductive elimination of H2 following the photolytic extrusion of CO from HFe(CO)4(-).

Introducing Water-Network-Assisted Proton Transfer for Boosted Electrocatalytic Hydrogen Evolution with Cobalt Corrole

Proton transfer is vital for many biological and chemical reactions. Hydrogen-bonded water-containing networks are often found in enzymes to assist proton transfer, but similar strategy has been rarely presented by synthetic catalysts. We herein report the Co corrole 1 with an appended crown ether unit and its boosted activity for the hydrogen evolution reaction (HER). Crystallographic and 1H NMR studies proved that the crown ether of 1 can grab water via hydrogen bonds. By using protic acids as proton sources, the HER activity of 1 was largely boosted with added water, while the activity of crown-ether-free analogues showed very small enhancement. Inhibition studies by adding 1) external 18-crown-6-ether to extract water molecules and 2) potassium ion or N-benzyl-n-butylamine to block the crown ether of 1 further confirmed its critical role in assisting proton transfer via grabbed water molecules. This work presents a synthetic example to boost HER through water-containing networks.

Pd/C-Catalyzed H2 Evolution from Tetrahydroxydiboron Hydrolysis

The production of H2 from non-fossil sources is a key research challenge to contributing solving the forthcoming energy problem. Aqueous solutions of tetrahydroxydiboron have very recently appeared as a H2 source, from which both hydrogen atoms are provided by water, in the presence of highly sophisticated nanocatalysts. Herein, commercial and cheap Pd/C is shown to be an efficient and recyclable catalyst for H2 evolution upon tetrahydroxydiboron hydrolysis. Graphic Abstract: [Figure not available: see fulltext.]

Hydrolysis of B2pin2 over Pd/C Catalyst: High Efficiency, Mechanism, and in situ Tandem Reaction

A facile and effective synthesis of H2 or D2 from Pd/C catalyzed hydrolysis of B2pin2 has first been developed. Among them, B2pin2 is frequently used for borylation reaction, and has rarely been used for hydrogen evolution. The kinetic isotope effects (KIEs) and tandem reaction for diphenylacetylene and norbornene hydrogenation have confirmed both two H atoms of H2 gas are provided from H2O. This is contrary to other boron compounds hydrolysis (including NH3BH3, NaBH4), which generates H2 with only one H atom provided by water and the other one by boron compounds. Note that the hydrolysis of B2pin2 in D2O also provides an easy and useful synthesis of D2.