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A step towards new nitrogen products
- donaldcuckman 6y agoHmm
- ttul 6y agohttps://www.nature.com/articles/s41586-020-2565-5 https://www.nature.com/articles/s41586-020-2565-5 The activation of abundant molecules such as hydrocarbons and atmospheric nitrogen (N2) remains a challenge because these molecules are often inert. The formation of carbon–nitrogen bonds from N2 typically has required reactive organic precursors that are incompatible with the reducing conditions that promote N2 reactivity1, which has prevented catalysis. Here we report a diketiminate-supported iron system that sequentially activates benzene and N2 to form aniline derivatives. The key to this coupling reaction is the partial silylation of a reduced iron–dinitrogen complex, followed by migration of a benzene-derived aryl group to the nitrogen. Further reduction releases N2-derived aniline, and the resulting iron species can re-enter the cyclic pathway. Specifically, we show that an easily prepared diketiminate iron bromide complex2 mediates the one-pot conversion of several petroleum-derived arenes into the corresponding silylated aniline derivatives, by using a mixture of sodium powder, crown ether, trimethylsilyl bromide and N2 as the nitrogen source. Numerous compounds along the cyclic pathway are isolated and crystallographically characterized, and their reactivity supports a mechanism for sequential hydrocarbon activation and N2 functionalization. This strategy couples nitrogen atoms from N2 with abundant hydrocarbons, and maps a route towards future catalytic systems.
- burfog 6y agoIt's "easily prepared", eh? Let's take a moment to appreciate the toxic, volatile, pyrophoric nature of this concoction: "sodium powder, crown ether, trimethylsilyl bromide and N2" Well, the N2 is probably fine. The pyrophoric sodium powder might even be a good thing, because it will cause an inferno long before the crown ether has a chance to form explosive peroxides.
- dnhz 6y agoThe reaction should be conducted in an oxygen-free, pure nitrogen atmosphere where those compounds should be safe to handle.
- deleted 6y ago[deleted]
- URSpider94 6y agoWhen it’s boiled to dryness, crown ether can produce peroxides that are unstable enough to explode on their own with shock or additional heat - no oxygen needed. It’s a not-uncommon mistake to make in a synthetic lab.
- dnhz 6y agoMy understanding is that evaporating solvent away doesn't form peroxides. Rather, as an ether ages, it can peroxidize. Removing the solvent concentrates the peroxides is all. Sure, it's a little tricky, but they're reporting results of chemistry research, which doesn't mean immediate real world application.
- krige 6y agosounds like a classic In The Pipeline "Things I Won't Work With" [0] tale [0] example: https://blogs.sciencemag.org/pipeline/archives/2010/02/23/things_i_wont_work_with_dioxygen_difluoride https://blogs.sciencemag.org/pipeline/archives/2010/02/23/th...
- zensavona 6y agoSounds super easy
- dnhz 6y agoIn a chemistry lab, it's not so tricky.
- DrAwdeOccarim 6y ago
- stevespang 6y agoaniline is a potent carcinogen.
- WantonQuantum 6y agoI find it interesting that I initially interpreted the headline “New nitrogen products are in the air” as a story about pollution. I.e., new nitrogen products (pollutants) have been detected in the atmosphere.
- chrisco255 6y agoAh well Nitrogen is the most abundant gas in the atmosphere so it's not by any stretch a pollutant.
- darkerside 6y agoI'm sure that was intentional. Effective clickbait.
- mc32 6y agoI saw it more as a pun. Unfortunately given the terrible practice of clickbait we no longer have the inclination to give puns the benefit of doubt.
- kovek 6y agoSame reaction for me earlier, and I didn’t have the time to look into it and had it on my mind since then. Should the title have “[not about pollutants]”?
- dang 6y agoOk, we've taken the nitrogen products out of the air in the title above.
- TedShiller 6y ago> The discovery comes from a team of Yale chemists who found a way to combine atmospheric nitrogen with benzene to make a chemical compound called aniline, which is a precursor to materials used to make an assortment of synthetic products. Ok, great. This is stated in a fairly neutral way. But one wonders if we are considering the negative effects of those synthetic products. That was the problem with plastics -- although revolutionary, there was a dearth of discourse about its negative effects, which we are feeling now.
- maxerickson 6y agoAniline is already a widely used industrial compound (used to make polyurethane). The novelty here is making it from atmospheric nitrogen.
- MertsA 6y agoNitrogen also makes up 2.6% of the Martian atmosphere and Nitrogen gas will likely be an important feedstock for future Martian ISRU plans.
- refurb 6y agoThose products already exist. This is just a new route to them.
- TedShiller 6y agoSometimes it's bad to have more routes to something, for example when the end result is plastic.
- throwaway0a5e 6y agoI'm not gonna lose any sleep over third world farmers realizing better crop yields using newly affordable fertilizer.
- SturgeonsLaw 6y agoIt's curious that plants haven't evolved to fix their own nitrogen, given their need for it and its abundance in the atmosphere
- wcoenen 6y agoAs far as I understand, the non-nitrogen atoms in the reaction are provided by benzene. Fun fact: benzene is so important in chemistry that it has two unicode code points, ⌬ and ⏣.
- thaumasiotes 6y agoWell, unicode doesn't have much to do with chemistry, or with importance. Those two symbols both long predate unicode (as you'd expect given the nature of unicode). The reason for the second symbol is that the positioning of the double bonds within the ring is underdetermined (and indeed, doesn't really exist) -- they are in a state of indeterminate flux much like the bonds in a molecule of ozone. The circle explicitly acknowledges that we can't really identify particular bonds as being the double bonds.
- EE84M3i 6y ago>Those two symbols both long predate unicode (as you'd expect given the nature of unicode). Yes, but notably they are not included in Unicode for compatibility with legacy character sets.
- thaumasiotes 6y agoAre they included in Unicode for any reason? They're not textual and don't make any sense (they are actually ill-formed[1]) as independent glyphs. [1] OK, they're not ill-formed if you really want to insert a miniature icon of a free benzene molecule into running text, but in chemistry you're mostly talking about benzene rings as a structural element in larger molecules, not molecular benzene.
- davidhyde 6y agoOne of the uses of aniline is hypergolic rockets although its pretty toxic stuff and as not used for large rockets anymore. Making test tube rockets with aniline, pretty interesting: https://www.youtube.com/watch?v=OszX18NLtrY https://www.youtube.com/watch?v=OszX18NLtrY
- chrisbrandow 6y agoCatalytic nitrogen fixation is one of the holy grails for chemists, so papers that get within spitting distance often get a lot of attention. This paper seems very interesting, but unless I’m mistaken it’s not catalytic and that’s a big caveat.
- nine_k 6y agoApparently none of the components of the mix get used up except the nitrogen and the benzene. It may be not one-step catalytic, but this should not be a problem. What am I missing?
- michieldotv 6y agoAtmospheric nitrogen is a big source of environmental and human harm in the Low Countries. The nitrogen deposits are literally smothering what little nature is left. It already led to a full-blown crisis in The Netherlands where construction sites were ordered to shut down. In Belgium, with the lack of effective national governance, the nitrogen problem is not being laying dormant. This kind of innovation hopefully bodes well for Belgium which has both an abundance of nitrogen _and_ a pervasive petrochemical industry.
- isthisnametaken 6y agoAtmospheric nitrogen sounds bad. And the Netherlands has to contend with some serious dihydrogen monoxide issues, too.
- thaumasiotes 6y ago> dihydrogen monoxide I always wanted to know why this name was picked over "hydrogen hydroxide".
- throwaway_pdp09 6y agoBecause people know carbon monoxide is toxic and will quickly make the false association.
- thaumasiotes 6y agoPeople know chlorine is toxic and salt is half chlorine... :/
- hechang1997 6y agoI think the article is talking about capturing inert N2 from atmosphere directly with benzene, not about nitrogen pollutants like NOx.
- wenc 6y agoI'm not sure if you are actually referring to nitrogen? Nitrogen (N2) constitutes 78% of the air we breathe. It's an inert, nontoxic gas and one of the least hazardous gases around -- the primary hazard being that of asphyxiation in closed spaces at high concentrations (due to displacement of O2). I'm not sure I follow that Belgium has an abundance of nitrogen. Every country in the world has an abundance of nitrogen - it's literally 78% of the air around us. To extract nitrogen, you pull air into a separation column and out comes N2. Any country in the world can do this. The two inputs are air and electricity (to power the compressor and other equipment).
- mkoryak 6y agoThere is a book which tells the story of fixing nitrogen from air and its a fanatic read: https://www.goodreads.com/book/show/3269091-the-alchemy-of-air https://www.goodreads.com/book/show/3269091-the-alchemy-of-a... its non-fiction