Anhydrous TEMPO-H: reactions of a good hydrogen atom donor with low-valent carbon centres

Publisher's version/PDFIn this paper, we report a novel synthesis of anhydrous 1-hydroxy-2,2,6,6-tetramethyl-piperidine (TEMPO-H). An X-ray crystal structure and full characterization of the compound are included. Compared to hydrated TEMPO-H, its anhydrous form exhibits improved stability and a differing chemical reactivity. The reactions of anhydrous TEMPO-H with a variety of low-valent carbon centres are described. For example, anhydrous TEMPO-H was reacted with 1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene (IMes), an unsaturated NHC. Crystals of CHNC[subscript 6H[subscript 2](CH[subscript 3])[subscript 3]][subscript 2]C...HO-(NC[subscript 5]H[subscript 6](CH[subscript 3])[subscript 4]), IMes...TEMPO-H, were isolated and a crystal structure determined. The experimental structure is compared to the results of theoretical calculations on the hydrogen-bonded dimer. Anhydrous TEMPO-H was also reacted with the saturated NHC, 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene (SIPr), giving the product [CH[subscript 2]Ni-Pr[subscript 2]C[subscript 6]H[subscript 3]][subscript 2]CH...O(NC[subscript 5]H[subscript 6](CH[subscript 3])[subscript 4]). In contrast, the reaction of hydrated TEMPO-H with 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene gave small amounts of the hydrolysis product, N-(2,6-diisopropylphenyl)-N-[2-(2,6-diisopropylphenylamino)ethyl]formamide. Finally, anhydrous TEMPO-H was reacted with (triphenylphosphoranylidene)ketene to generate Ph[subscript 3]PC(H)C(=O)O(NC[subscript 5]H[subscript 6](CH[subscript 3])[subscript 4]). A full characterization of the product, including an X-ray crystal structure, is described

Mono- and bis-imidazolidinium ethynyl cations and the reduction of the latter to give an extended bis-1,4-([3]cumulene)-p-carbo-quinoid system

Sherpa Romeo yellow journal. This is the peer reviewed version. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived VersionsAn extended π-system containing two [3]cumulene fragments separated by a p-carbo-quinoid and stabilized by two capping N-heterocyclic carbenes (NHCs) has been prepared. Mono- and bis-imidazolidinium ethynyl cations have also been synthesized from the reaction of an NHC with phenylethynyl bromide or 1,4bis(bromoethynyl)benzene. Cyclic voltammetry coupled with synthetic and structural studies showed that the dication is readily reduced to a neutral, singlet bis-1,4-([3]cumulene)-p-carbo-quinoid due to the πaccepting properties of the capping NHCsYe

Simple Ion–Gas Mixtures as a Source of Key Molecules Relevant to Prebiotic Chemistry

Very simple chemistry can result in the rapid and high-yield production of key prebiotic inorganic molecules. The two reactions investigated here involve such simple systems, (a) carbon disulfide (CS2) and acetate (CH3COO¯) and (b) sulfur dioxide (SO2) and formate (HCOO¯). They have been carried out under non-aqueous conditions, either in an organic solvent or with a powdered salt exposed to the requisite gas. Under such dry conditions the first reaction generated the thioacetate anion [CH3COS]¯ while the second produced the radical [SO2·]¯anion. Anhydrous conditions are not rare and may have arisen on the early earth at sites where an interface between different phases (liquid/gas or solid/gas) could be generated. This is one way to rationalize the formation of molecules and ions (such as we have produced) necessary in the prebiotic world. Interpretation of our results provides insight into scenarios consistent with the more prominent theories of abiogenesis

Lactic acid demineralization of green crab (Carcinus maenas) shells: effect of reaction conditions and isolation of an unusual calcium complex

Chitin and chitosan are potentially useful and environmentally friendly biopolymers with a wide range of value-added applications. Effective and green technologies for isolation of these materials are potentially important. Here, we report the use of lactic acid for the demineralization of green crab shells. Green crab shells and lactic acid, produced during cheese making, are two waste streams that could be tapped for large-scale chitin and chitosan processing. We have studied the effect of concentration and temperature on the demineralization of green crab shells. An unusual calcium lactate/lactic acid complex was also isolated and crystallographically characterized. The results have implications not only for the use of weak acids in the isolation of chitin and chitosan but also for the use of lactic acid as a solvent in green chemistry