| |||
Names | |||
---|---|---|---|
Preferred IUPAC name sulfur mononitride | |||
Systematic IUPAC name Azaniumylsulfanidylidyne | |||
Other names
| |||
Identifiers | |||
3D model (JSmol) | |||
Abbreviations | (NS)(.) | ||
ChEBI | |||
ChemSpider | |||
660 | |||
PubChem CID | |||
CompTox Dashboard (EPA) | |||
| |||
| |||
Properties | |||
NS | |||
Molar mass | 46.07 g·mol−1 | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). |
Sulfur mononitride is an inorganic compound with the molecular formula SN. It is the sulfur analogue of and isoelectronic to the radical nitric oxide, NO. It was initially detected in 1975, in outer space in giant molecular clouds and later the coma of comets. [1] This spurred further laboratory studies of the compound. Synthetically, it is produced by electric discharge in mixtures of nitrogen and sulfur compounds, or combustion in the gas phase and by photolysis in solution. [2]
The NS radical is a highly transient species, with a lifetime on the order of milliseconds, but it can be observed spectroscopically over short periods of time through several methods of generation. NS is too reactive to isolate as a solid or liquid, and has only been prepared as a vapor in low pressure or low-temperature matrices due to its tendency to rapidly oligomerize to more stable, diamagnetic species. [3]
Transmission of electric discharge through a glass tube with quartz windows containing a mixture of nitrogen and sulfur vapor (rigorously free of oxygen) results in the spectrum of emitted light gaining bands consistent with the formation of NS. [4]
Passing a mixture of gaseous N2 and S2Cl2 through the side arm of an absorption cell undergoing microwave discharge produces NS. Infrared diode laser spectroscopy taken using this method allowed for derivation of the equilibrium rotational constant, and therefore calculation of the equilibrium bond length as 1.4940 Å. [5]
With low pressure microwave discharge of elemental nitrogen and sulfur, followed by low temperature trapping in argon matrices, one obtains a mixture of products including NS, NNS, SNS, and NSS. By adding excess sulfur, SSNS is also produced. [6]
Methane was premixed with fuel in the form of either O2, N2O, or air and burned at ambient pressure. The source of nitrogen was introduced by addition of 1-5 mole% NH3 gas and sulfur by 0.01-0.5 mol% H2S or SF6 gas. A steady state concentration of NS within the flame front is observed by laser-induced fluorescence (LIF) spectrum. [7]
N4S4 (g) was obtained by the following reaction:
Removal of byproducts leaves only N4S4 in toluene, which is through a gas inlet pipe into the reaction cell. [8]
Another common method for bulk production of N4S4 production involves the condensation of ammonia with S2Cl2 in inert solvents, [3] however the former method was chosen to avoid isolation of N4S4 in its reactive, solid state.
The NS radical was subsequently identified by LIF spectrum as the product of photolysis of N4S4 (g) by a 248 nm laser. [8]
Aerated solutions of Cr(CH3CN)5(NS)2+ are highly photoactive and prone to rapid decomposition. Deaerated solutions of Cr(CH3CN)5(NS)2+ in acetonitrile are stable as long as they are kept in the dark. Continuous photolysis using 366 nm light is slow, while using a 355 nm pulsed laser results in faster labilization of NS. [9]
Evidence suggests that NS can react with itself to reach N2S2, N4S4, and polymers of the form (NS)x. (NS)x forms from polymerization of cyclo-N2S2. [3]
Trans-NSSN results from direct dimerization of NS. [3]
N3S3 has been observed through photoelectron spectroscopy of vapors of the (SN)x, polymer, but has not yet been characterized further. Attempts to produce N3S3 by oxidation of [PPN][S3N3] were unsuccessful. [10] Its theorized that rapid dimerization to (N3S3)2 will disproportionate irreversibly to N4S4 and N2S2. [3]
The radical decay time of NS alone is on the order of 1-3 ms. As evident by no change to this decay time upon addition of NO or O2 at ambient temperatures, the NS radical is unreactive with NO and O2. However, rapid, first-order decay is observed with the addition of NO2. This reaction is proposed to proceed through various intermediates, ultimately reaching final products of N2 and SO2. [8] This rapid reaction occurs with a rate constant of k = (2.54 ± 0.12) × 10−11 cm3 molecules−1 s−1 at 295 K. By use of Density Functional Theory based computational calculations, the minima and transition states of the potential energy surface of this reaction have been predicted. [8]
Within the inner coma of comets, many reactions are theorized to be relevant to the formation and reactivity of the NS radical. [11]
As a ligand, NS acts as a σ-donor and π-acceptor, forming metal-thionitrosyl complexes. Transition-metal thionitrosyl complexes have been prepared by the following procedures: [12]
From X-ray crystallography of many of such metal-thionitrosyl complexes, one can observe that the M-N-S bond angle is nearly linear, suggesting sp hybridization about N. Short M-N distances and long N-S distances reflect the resonance structure of M=N=S having greater contribution than M-N≡S. [12]
Typical v(NS) IR stretching frequencies are approximately 1065 cm−1 for low-valent transition metal complexes and around 1390 cm−1 in the high valent cases, whereas the free gas-phase radical exhibits a 1204 cm−1 signal. [3]
The electronic structures of Fe(S2CNMe2)2(NE), where E=O, S, or Se were calculated using Density Functional Theory methods. It was found that the large Mulliken spin density remained concentrated on the Fe(NE) core and Fe-N distances experienced little change from the chalcogen atom used. The HOMO of both nitrosyl and thionitrosyl complexes retained 1a1 (dz2) character. The small changes in the energies of the spin orbitals of the complexes, particularly the decreased energetic gap between 2b2 and 1b1 and 2b1 and 1b1 orbitals is attributed to NS being a weaker π-acceptor than NO. [9]
When a spin-trapping agent, such as Fe(S2CNEt2)2 is present during the photolysis of Cr(CH3CN)5(NS)2+, new S=1/2 EPR bands are observed, attributed to the formation of Fe(S2CNEt2)2(NS), and the signal from Cr(CH3CN)5(NS)2+ disappears. This suggests that the NS radical has transferred from the chromium complex to the iron complex. [9]
This was particularly significant as it was the first controlled and well-characterized reactivity of NS in solution. Further, it showed the potential for similar reactivity in known reactions with NO, such as use of this iron dithiocarbamate complex. [3]
The valence electrons of this compound match those of nitric oxide. Sulfur mononitride can be described as some average of a set of resonance structures. The singly bonded structure (first resonance structure shown) has little contribution. The formal bond order is considered to be 2.5.
The decreasing electronegativity with increasingly heavy chalcogenides leads to a reversal of the dipole. In NO, oxygen is the more electronegative element. In NS, nitrogen is more electronegative. The NS radical is significantly more unstable and prone to catenation than NO. [3]
NO | NS | NSe | |
---|---|---|---|
△fH°, kJ·mol−1 | +90.24 | +283.4 | - |
△fG°, kJ·mol−1 | +86.57 | +217.2 | - |
S° 273, J/deg | +207.5/273 K | +222.093/298 K | - |
B.D.E. | 627.6 | 463±24 | 370 Cal |
d(N-E), Å | 1.1517 | 1.4938 | 1.6634 |
Bond order | 2.5 | 2.5 | 2.5 |
Molecules in distant astronomical regions can be identified based on their unique rotational transitions, of which the corresponding microwave frequencies are detectable by antennae on Earth. The presence of interstellar sulfur mononitride was first reported in 1975 by back to back letters published in the Astrophysical Journal.
Interstellar NS was first identified in the giant molecular cloud Sagittarius B2 (Sgr B2). Its presence was reported in two concurrent articles. Measurements conducted with the National Radia Astronomy Observatory telescope at Kitt Peak, Arizona, picked up millimeter-wavelength radiation in Sgr B2 attributed to c-state transitions of NS in the 2Π1/2 state from J=5/2 to J=3/2 at 115.16 GHz. [15] This assignment was confirmed by measurements conducted at University of Texas Millimeter Wave Observatory on Mount Locke as well, demonstrating J=5/2 to J=3/2 c-state and d-state transitions at 115.16 GHz and 115.6 GHz, respectively. Hyperfine interactions arise from 14N magnetic and electric-quadrupole moments. [16]
NS has been detected in regions responsible for forming massive stars, such as giant molecular clouds like Sg B2 and cold, dark clouds such as L134N and TMC-1. One survey found NS in 12 out of 14 GMC studied, additionally observing the J=7/2 to J=5/2 and J=3/2 to J=1/2 transitions at 161 and 69 GHz, respectively. The abundance of NS in these regions was approximated based on the ratio of observed to intrinsic hyperfine line strengths as well as modeling using a statistical equilibrium program, finding low abundance in all except the Orion molecular cloud. [17]
NS was also observed in the coma of the comets Hyakutake and Hale-Bopp. It's believed that the observed abundance is higher than gas-phase, ion-molecule models due to an unidentified species X-NS photo-dissociating to release NS. [11]
Detection of NS at steady state concentration in the reaction zone of the combustion of methane doped with ammonia and a fuel sulfur such as H2S suggests that NS may be an important reactive intermediate in burning of hydrocarbon flames in a reducing atmosphere, which is relevant to coal pyrolysis and combustion. [7]
Fossil fuels contain bound nitrogen, which releases elevated levels of nitric oxide emissions during combustion. NOx emissions can be controlled by denitrification of the fuel source, combustion chamber modification, or both. One developing technique is the reburning of NOx, which is reduced to N2. These fuels also contain variable amounts of sulfur, which is oxidized to SO2. Therefore, understanding the reactivity of NO and SO2 is crucial to the process of reburning. The experimental apparatus to test this involved a primary flame for producing combustion products, which were mixed with NO and SO2 to mimic coal burning byproducts. This mixture was fed into the burner at atmospheric pressure. 1-2% decrease in NOx concentration is observed at various percentages of total fuel inlet (reburn ratio) in the presence of 0.1% SO2, which is attributed to the formation of H2S, HS, and the resulting reaction with NO, giving rise to NS. Reaction: HS + NO > NS + OH. [18]
Inorganic chemistry deals with synthesis and behavior of inorganic and organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, medications, fuels, and agriculture.
An oxide is a chemical compound containing at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– ion with oxygen in the oxidation state of −2. Most of the Earth's crust consists of oxides. Even materials considered pure elements often develop an oxide coating. For example, aluminium foil develops a thin skin of Al2O3 that protects the foil from further oxidation.
Nitric oxide is a colorless gas with the formula NO. It is one of the principal oxides of nitrogen. Nitric oxide is a free radical: it has an unpaired electron, which is sometimes denoted by a dot in its chemical formula. Nitric oxide is also a heteronuclear diatomic molecule, a class of molecules whose study spawned early modern theories of chemical bonding.
Nitrogenases are enzymes (EC 1.18.6.1EC 1.19.6.1) that are produced by certain bacteria, such as cyanobacteria (blue-green bacteria) and rhizobacteria. These enzymes are responsible for the reduction of nitrogen (N2) to ammonia (NH3). Nitrogenases are the only family of enzymes known to catalyze this reaction, which is a key step in the process of nitrogen fixation. Nitrogen fixation is required for all forms of life, with nitrogen being essential for the biosynthesis of molecules (nucleotides, amino acids) that create plants, animals and other organisms. They are encoded by the Nif genes or homologs. They are related to protochlorophyllide reductase.
In organic chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is R−:C−R' or R=C: where the R represents substituents or hydrogen atoms.
In chemistry, a nitrene or imene is the nitrogen analogue of a carbene. The nitrogen atom is uncharged and univalent, so it has only 6 electrons in its valence level—two covalent bonded and four non-bonded electrons. It is therefore considered an electrophile due to the unsatisfied octet. A nitrene is a reactive intermediate and is involved in many chemical reactions. The simplest nitrene, HN, is called imidogen, and that term is sometimes used as a synonym for the nitrene class.
The iron cycle (Fe) is the biogeochemical cycle of iron through the atmosphere, hydrosphere, biosphere and lithosphere. While Fe is highly abundant in the Earth's crust, it is less common in oxygenated surface waters. Iron is a key micronutrient in primary productivity, and a limiting nutrient in the Southern ocean, eastern equatorial Pacific, and the subarctic Pacific referred to as High-Nutrient, Low-Chlorophyll (HNLC) regions of the ocean.
Organosulfur compounds are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur derivatives, e.g., saccharin. Nature abounds with organosulfur compounds—sulfur is vital for life. Of the 20 common amino acids, two are organosulfur compounds, and the antibiotics penicillin and sulfa drugs both contain sulfur. While sulfur-containing antibiotics save many lives, sulfur mustard is a deadly chemical warfare agent. Fossil fuels, coal, petroleum, and natural gas, which are derived from ancient organisms, necessarily contain organosulfur compounds, the removal of which is a major focus of oil refineries.
A transition metal carbene complex is an organometallic compound featuring a divalent organic ligand. The divalent organic ligand coordinated to the metal center is called a carbene. Carbene complexes for almost all transition metals have been reported. Many methods for synthesizing them and reactions utilizing them have been reported. The term carbene ligand is a formalism since many are not derived from carbenes and almost none exhibit the reactivity characteristic of carbenes. Described often as M=CR2, they represent a class of organic ligands intermediate between alkyls (−CR3) and carbynes (≡CR). They feature in some catalytic reactions, especially alkene metathesis, and are of value in the preparation of some fine chemicals.
The Barton–McCombie deoxygenation is an organic reaction in which a hydroxy functional group in an organic compound is replaced by a hydrogen to give an alkyl group. It is named after British chemists Sir Derek Harold Richard Barton and Stuart W. McCombie.
The 18-electron rule is a chemical rule of thumb used primarily for predicting and rationalizing formulas for stable transition metal complexes, especially organometallic compounds. The rule is based on the fact that the valence orbitals in the electron configuration of transition metals consist of five (n−1)d orbitals, one ns orbital, and three np orbitals, where n is the principal quantum number. These orbitals can collectively accommodate 18 electrons as either bonding or non-bonding electron pairs. This means that the combination of these nine atomic orbitals with ligand orbitals creates nine molecular orbitals that are either metal-ligand bonding or non-bonding. When a metal complex has 18 valence electrons, it is said to have achieved the same electron configuration as the noble gas in the period, lending stability to the complex. Transition metal complexes that deviate from the rule are often interesting or useful because they tend to be more reactive. The rule is not helpful for complexes of metals that are not transition metals. The rule was first proposed by American chemist Irving Langmuir in 1921.
Metal nitrosyl complexes are complexes that contain nitric oxide, NO, bonded to a transition metal. Many kinds of nitrosyl complexes are known, which vary both in structure and coligand.
The Hofmann–Löffler reaction (also referred to as Hofmann–Löffler–Freytag reaction, Löffler–Freytag reaction, Löffler–Hofmann reaction, as well as Löffler's method) is an organic reaction in which a cyclic amine 2 (pyrrolidine or, in some cases, piperidine) is generated by thermal or photochemical decomposition of N-halogenated amine 1 in the presence of a strong acid (concentrated sulfuric acid or concentrated CF3CO2H). The Hofmann–Löffler–Freytag reaction proceeds via an intramolecular hydrogen atom transfer to a nitrogen-centered radical and is an example of a remote intramolecular free radical C–H functionalization.
Disulfur monoxide or sulfur suboxide is an inorganic compound with formula S2O, one of the lower sulfur oxides. It is a colourless gas and condenses to give a roughly dark red coloured solid that is unstable at room temperature.
Sulfanyl (HS•), also known as the mercapto radical, hydrosulfide radical, or hydridosulfur, is a simple radical molecule consisting of one hydrogen and one sulfur atom. The radical appears in metabolism in organisms as H2S is detoxified. Sulfanyl is one of the top three sulfur-containing gasses in gas giants such as Jupiter and is very likely to be found in brown dwarfs and cool stars. It was originally discovered by Margaret N. Lewis and John U. White at the University of California in 1939. They observed molecular absorption bands around 325 nm belonging to the system designated by 2Σ+ ← 2Πi. They generated the radical by means of a radio frequency discharge in hydrogen sulfide. HS• is formed during the degradation of hydrogen sulfide in the atmosphere of the Earth. This may be a deliberate action to destroy odours or a natural phenomenon.
Diiminopyridines are a class of diimine ligands. They featuring a pyridine nucleus with imine sidearms appended to the 2,6–positions. The three nitrogen centres bind metals in a tridentate fashion, forming pincer complexes. Diiminopyridines are notable as non-innocent ligand that can assume more than one oxidation state. Complexes of DIPs participate in a range of chemical reactions, including ethylene polymerization, hydrosilylation, and hydrogenation.
FeMoco (FeMo cofactor) is the primary cofactor of nitrogenase. Nitrogenase is the enzyme that catalyzes the conversion of atmospheric nitrogen molecules N2 into ammonia (NH3) through the process known as nitrogen fixation. Studying FeMoco's role in the reaction mechanism for nitrogen fixation is a potential use case for quantum computers. Even limited quantum computers could enable better simulations of the reaction mechanism.
In chemistry, the selection rule formally restricts certain reactions, known as spin-forbidden reactions, from occurring due to a required change between two differing quantum states. When a reactant exists in one spin state and the product exists in a different spin state, the corresponding reaction will have an increased activation energy when compared to a similar reaction in which the spin states of the reactant and product are isomorphic. As a result of this increased activation energy, a decreased rate of reaction is observed.
Germyl, trihydridogermanate(1-), trihydrogermanide, trihydridogermyl or according to IUPAC Red Book: germanide is an anion containing germanium bounded with three hydrogens, with formula GeH−3. Germyl is the IUPAC term for the –GeH3 group. For less electropositive elements the bond can be considered covalent rather than ionic as "germanide" indicates. Germanide is the base for germane when it loses a proton.
A transition metal sulfoxide complex is a coordination complex containing one or more sulfoxide ligands. The inventory is large.