CH CN Research Articles

Rearrangement of a P4 Butterfly Complex-The Formation of a Homoleptic Phosphorus-Iron Sandwich Complex.

The versatile coordination behavior of the P4 butterfly complex [{Cp'''Fe(CO)2 }2 (μ,η1:1 -P4 )] (1, Cp'''=η5 -C5 H2t Bu3 ) towards different iron(II) compounds is presented. The reaction of 1 with [FeBr2 ⋅dme] (dme=dimethoxyethane) leads to the chelate complex [{Cp'''Fe(CO)2 }2 (μ3 ,η1:1:2 -P4 ){FeBr2 }] (2), whereas, in the reaction with [Fe(CH3 CN)6 ][PF6 ]2 , an unprecedented rearrangement of the P4 butterfly structural motif leads to the cyclo-P4 moiety in {(Cp'''Fe(CO)2 )2 (μ3 ,η1:1:4 -P4 )}2 Fe][PF6 ]2 (3). Complex 3 represents the first fully characterized "carbon-free" sandwich complex containing cyclo-P4 R2 ligands in a homoleptic-like iron-phosphorus-containing molecule. Alternatively, 2 can be transformed into 3 by halogen abstraction and subsequent coordination of 1. The additional isolated side products, [{Cp'''Fe(CO)2 }2 (μ3 ,η1:1:2 -P4 ){Cp'''Fe(CO)}][PF6 ] (4) and [{Cp'''Fe(CO)2 }2 (μ3 ,η1:1:4 -P4 ){Cp'''Fe}][PF6 ] (5), give insight into the stepwise activation of the P4 butterfly moiety in 1.

Design of Na+ -Selective Fluorescent Probes: A Systematic Study of the Na+ -Complex Stability and the Na+ /K+ Selectivity in Acetonitrile and Water.

There is a tremendous demand for highly Na+ -selective fluoroionophores to monitor the top analyte Na+ in life science. Here, we report a systematic route to develop highly Na+ /K+ selective fluorescent probes. Thus, we synthesized a set of fluoroionophores 1, 3, 4, 5, 8 and 9 (see Scheme ) to investigate the Na+ /K+ selectivity and Na+ - complex stability in CH3 CN and H2 O. These Na+ -probes bear different 15-crown-5 moieties to bind Na+ stronger than K+ . In the set of the diethylaminocoumarin-substituted fluoroionophores 1-5, the following trend of fluorescence quenching 1>3>2>4>5 in CH3 CN was observed. Therefore, the flexibility of the aza-15-crown-5 moieties in 1-4 determines the conjugation of the nitrogen lone pair with the aromatic ring. As a consequence, 1 showed in CH3 CN the highest Na+ -induced fluorescence enhancement (FE) by a factor of 46.5 and a weaker K+ induced FE of 3.7. The Na+ -complex stability of 1-4 in CH3 CN is enhanced in the following order of 2>4>3>1, assuming that the O-atom of the methoxy group in the ortho-position, as shown in 2, strengthened the Na+ -complex formation. Furthermore, we found for the N-(o-methoxyphenyl)aza-15-crown-5 substituted fluoroionophores 2, 8 and 9 in H2 O, an enhanced Na+ -complex stability in the following order 8>2>9 and an increased Na+ /K+ selectivity in the reverse order 9>2>8. Notably, the Na+ -induced FE of 8 (FEF=10.9), 2 (FEF=5.0) and 9 (FEF=2.0) showed a similar trend associated with a decreased K+ -induced FE [8 (FEF=2.7)>2 (FEF=1.5)>9 (FEF=1.1)]. Here, the Na+ -complex stability and Na+ /K+ selectivity is also influenced by the fluorophore moiety. Thus, fluorescent probe 8 (Kd =48 mm) allows high-contrast, sensitive, and selective Na+ measurements over extracellular K+ levels. A higher Na+ /K+ selectivity showed fluorescent probe 9, but also a higher Kd value of 223 mm. Therefore, 9 is a suitable tool to measure Na+ concentrations up to 300 mm at a fluorescence emission of 614 nm.

On the Importance of π-Hole Beryllium Bonds: Theoretical Study and Biological Implications.

In this study, the ability of beryllium compounds to establish π-hole bonding interactions has been evaluated at the RI-MP2/def2-TZVPD level of theory. A search of the Protein Data Bank revealed some X-ray crystal structures in which BeF3- moieties act as electron-acceptor entities. We have used [Mg(BeF3 )(HCOO)] (1) as a π-hole bond donor and CO, CH3 CN, NH3 , O(CH3 )2 , S(CH3 )2 , H3 PO, and glycine as electron-rich entities. In all cases, favorable binding energies were obtained, reflecting the attractive nature of the interaction involving the trivalent beryllium atom (-BeF3 moiety). In addition, we have used Bader's theory of "atoms in molecules" and noncovalent interaction (NCI) plot analysis to further investigate and characterize the π-hole complexes described herein. To the best of our knowledge, π-hole interactions involving beryllium have not hitherto been described in the literature.

Synthesis of Functionalized Cyclopentene Derivatives from Vinyldiazo Compounds and Vinylazides through Sequential Copper-Promoted [3+2] Cycloaddition/Azide Rearrangement.

The reaction of vinylazides with alkenyldiazo compounds in the presence of [Cu(CH3 CN)4 ][BF4 ] provided cyclopentene derivatives with retention of the azide functionality. This process likely involves a sequence comprising: 1) decomposition of the diazo component with generation of a copper alkenylcarbene species; 2) stepwise regioselective [3+2] cycloaddition; 3) allylic azide rearrangement. This method is compatible with a broad range of substrates. We also show that the azide-containing cycloadducts can be efficiently converted into the corresponding amine and triazole derivatives.

Reactions of Dilithium Dibenzopentalenides with Cr(CO)3 (CH3 CN)3 : Unexpected Formation of a Cubic Tetramer of an Anionic Hydrodibenzopentalenyl Complex.

To explore the coordination chemistry of dibenzopentalene dianion, reactions of two dilithium dibenzopentalenides having different silyl substituents with Cr(CO)3 (CH3 CN)3 were investigated. The products were unexpected anionic complexes, [Li(Et2 O)]+ [Cr(η5 -9-hydrodibenzopentalenyl)(CO)3 ]- . The proton at the 9-position is derived from Cr(CO)3 (CH3 CN)3 , as evidenced by the use of Cr(CO)3 (CD3 CN)3 . The X-ray diffraction analysis revealed that the chromium is coordinated by an anionic five-membered ring of the pentalene skeleton, and the lithium atom is coordinated by oxygen atoms of the carbonyl groups. The complexes form a dimer or a cage-like tetramer via carbonyl-lithium interactions, depending on the bulk of the silyl groups. The cubic tetramer appears to retain its cage structure in nonpolar solvents such as benzene.

Guest-induced Assembly of Bis(thiosemicarbazonato) Zinc(II) Coordination Nanotubes.

A ZnII complex of the dianionic tetradentate ligand formed by deprotonation of glyoxal-bis(4-phenyl-3-thiosemicarbazone) (H2 gtsp) is a [3+3] trinuclear triangular prism. Recrystallization of this complex in the presence of either CO2 , CS2 , or CH3 CN leads to the formation of [4+4] open-ended charge-neutral tetranuclear coordination nanotubes, approximately 2 nm in length and with internal dimensions large enough to accommodate linear guest molecules, which serve to template their formation. Upon removal of the templating molecules the nanotubes demonstrated reversible sorption of CO2 with an isosteric enthalpy of sorption of 28 kJ mol-1 at low loading.

Electrochemical Formation of FeV (O) and Mechanism of Its Reaction with Water During O-O Bond Formation.

A detailed electrochemical investigation of a series of iron complexes (biuret-modified tetraamido iron macrocycles FeIII -bTAML), including the first electrochemical generation of FeV (O), and demonstration of their efficacy as homogeneous catalysts for electrochemical water oxidation (WO) in aqueous medium are reported. Spectroelectrochemical and mass spectral studies indicated FeV (O) as the active oxidant, formed due to two redox transitions, which were assigned as FeIV (O)/FeIII (OH2 ) and FeV (O)/FeIV (O). The spectral properties of both of these high-valent iron oxo species perfectly match those of their chemically synthesised versions, which were thoroughly characterised by several spectroscopic techniques. The O-O bond-formation step occurs by nucleophilic attack of H2 O on FeV (O). A kinetic isotope effect of 3.2 indicates an atom-proton transfer (APT) mechanism. The reaction of chemically synthesised FeV (O) in CH3 CN and water was directly probed by electrochemistry and was found to be first-order in water. The pKa value of the buffer base plays a critical role in the rate-determining step by increasing the reaction rate several-fold. The electronic effect on redox potential, WO rates, and onset overpotential was studied by employing a series of iron complexes. The catalytic activity was enhanced by the presence of electron-withdrawing groups on the bTAML framework. Changing the substituents from OMe to NO2 resulted in an eightfold increase in reaction rate, while the overpotential increased threefold.

ESI activity of Br⁻, BF₄⁻ , ClO₄⁻ and BPh₄⁻ anions in the presence of Li⁺ and NBu⁴⁺ counter-ions.

To improve our understanding of the electrospray ionization (ESI) process, we have subjected equimolar mixtures of salts A+ X- (A+ =Li+ , NBu4+ ; X- =Br- , ClO4- , BF4- , BPh4- ) in different solvents (CH3 CN, tetrahydrofuran, CH3 OH, H2 O) to negative-ion mode ESI and analyzed the relative ESI activity of the different anionic model analytes. The ESI activity of the large and hydrophobic BPh4- ion greatly exceeds that of the smaller and more hydrophilic anions Br- , ClO4- and BF4- , which we ascribe to its higher surface activity. Moreover, the ESI activity of the anions is modulated by the action of the counter-ions and their different tendency toward ion pairing. The tendency toward ion pairing can be reduced by the addition of the chelating ligands 12-crown-4 and 2.2.1 cryptand and is, although to a smaller degree, further influenced by the variation of the solvent. Complementary electrical conductivity measurements afford additional information on the interactions of the ionic constituents of the sample solutions. Copyright © 2017 John Wiley & Sons, Ltd.

Dimensionally Controlled Assembly of an External Stimuli-Responsive [Co2 Fe2 ] Complex into Supramolecular Hydrogen-Bonded Networks.

A stimuli-responsive tetranuclear complex was assembled into new aggregates with controllable dimensionality through directional hydrogen bonds (HBs). A cyanide-bridged tetranuclear complex cation, [Co2 Fe2 (CN)6 (tp*)2 (bpy*)4 ]2+ (abbreviated to 12+ ) (tp*=hydrotris(3,5-dimethylpyrazol-1-yl)borate and bpy*=4,4'-di-methyl-2,2'-bipyridine) has two terminal cyanide nitrogens and acts as a hydrogen-bond acceptor (HBA) with a linear bridging mode. Co-crystallization of 12+ with p-hydroquinone (H2 Q), a hydrogen-bond donor (HBD) with two donor sites, led to a one-dimensional aggregate, 1(BPh4 )2 ⋅(H2 Q)⋅2 H2 O (2), while a two-dimensional sheet with a honeycomb structure, 13 (PF6 )6 ⋅(H3 PG)2 ⋅4 CH3 CN⋅8 H2 O (3), was obtained by co-crystallization with phloroglucinol (H3 PG) acting as a three-way structure-directing HBD. Magnetic measurements revealed that 2 and 3 exhibited thermal and light-induced electron-transfer-coupled spin transitions (ETCSTs).

Mechanism of the Copper/TEMPO-Catalyzed Aerobic Oxidation of Alcohols.

Identifying the mechanism of a catalytic reaction is paramount for designing new and improved catalysts. Several alternative catalytic cycles for the copper/2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)-catalyzed aerobic oxidation of alcohols to the corresponding aldehydes or ketones were examined using DFT at the SMD(CH3 CN)-RIJCOSX-DSD-PBEB95/def2-TZVP//DF-PBED3BJ /def2-SVP level of theory. A catalytic cycle in which TEMPO remains coordinated to copper throughout was identified as the most likely mechanism. There are three components to the catalytic cycle: 1) hydrogen transfer from the alkoxyl ligand to coordinated TEMPO, 2) oxygen activation with formation of a peroxo complex, and 3) alcohol activation with transfer of the OH proton to the peroxo ligand. The oxidation takes place via a six-membered intramolecular hydrogen-transfer transition state. Importantly, this is not the rate-determining step, which instead involves oxygen activation and/or the initial alcohol activation.

Continuous Flow Homolytic Aromatic Substitution with Electrophilic Radicals: A Fast and Scalable Protocol for Trifluoromethylation.

We report an operationally simple and rapid continuous flow radical C-C bond formation under Minisci-type reaction conditions. The transformations are performed at or below room temperature employing hydrogen peroxide (H2 O2 ) and dimethylsulfoxide (DMSO) as reagents in the presence of an FeII catalyst. For electron-rich aromatic and heteroaromatic substrates, C-C bond formation proceeds satisfactorily with electrophilic radicals including . CF3 , . C4 F9 , . CH2 CN, and . CH2 CO2 Et. In contrast, electron-poor substrates exhibit minimal reactivity. Importantly, trifluoromethylations and nonafluororobutylations using CF3 I and C4 F9 I as reagents proceed exceedingly fast with high conversion for selected substrates in residence times of a few seconds. The attractive features of the present process are the low cost of the reagents and the extraordinarily high reaction rates. The direct application of the protocol to dihydroergotamine, a complex ergot alkaloid, yielded the corresponding trifluoromethyl ergoline derivative within 12 seconds in a continuous flow microreactor on a 0.6 kg scale. The trifluoromethyl derivative of dihydroergotamine is a promising therapeutic agent for the treatment of migraines.

The Uranium(VI) Oxoazides [UO2 (N3 )2 ⋅CH3 CN], [(bipy)2 (UO2 )2 (N3 )4 ], [(bipy)UO2 (N3 )3 ]- , [UO2 (N3 )4 ]2- , and [(UO2 )2 (N3 )8 ]4.

The reaction between [UO2 F2 ] and an excess of Me3 SiN3 in acetonitrile solution results in fluoride-azide exchange and the uranium(VI) dioxodiazide adduct [UO2 (N3 )2 ⋅CH3 CN] was isolated in quantitative yield. The subsequent reaction of [UO2 (N3 )2 ⋅CH3 CN] with 2,2'-bipyridine (bipy) resulted in the formation of the azido-bridged binuclear complex [(bipy)2 (UO2 )2 (N3 )4 ]. The triazido anion [(bipy)UO2 (N3 )3 ]- was obtained by the reaction of [UO2 (N3 )2 ⋅CH3 CN] with stoichiometric amounts of bipy and the ionic azide [PPh4 ][N3 ]. The reaction of [UO2 (N3 )2 ] with two equivalents of the [PPh4 ][N3 ] resulted in the formation of the mononuclear tetraazido anion [UO2 (N3 )4 ]2- as well as the azido-bridged binuclear anion [(UO2 )2 (N3 )8 ]4- . The novel uranium oxoazides were characterized by their vibrational spectra and in the case of [(bipy)2 (UO2 )2 (N3 )4 ]⋅CH3 CN, [PPh4 ][(bipy)UO2 (N3 )3 ], [PPh4 ]2 [UO2 (N3 )4 ], [PPh4 ]2 [UO2 (N3 )4 ]⋅2CH3 CN, and [PPh4 ]4 [(UO2 )2 (N3 )8 ]⋅4CH3 CN by their X-ray crystal structures.

Chiral Self-Recognition between Stereogenic Tetrapalladium Units Affording Pd8 Chains Supported by Homochiral Tetraphosphines.

By using a chiral tetraphosphine, rac-bis[(diphenylphosphinomethyl)phenylphosphino]methane (rac-dpmppm), linear octapalladium chains were synthesized as discrete molecules of [Pd8 (μ-rac-dpmppm)4 L2 ](BF4 )4 (L=CH3 CN, dmf, XylNC), [Pd8 (μ-rac-dpmppm)4 ](BF4 )4 , and [Pd8 (μ-rac-dpmppm)4 (Cl)2 ](BF4 )2 , which are stable in the solution states and characterized by spectroscopic and crystallographic methods to reveal the octapalladium chains supported by homochiral four tetraphosphines. Variable-temperature NMR studies for a 1:1 mixture of [Pd8 (μ-rac-dpmppm)4 (dmf)2 ](BF4 )4 and [Pd8 (μ-meso-dpmppm)4 (dmf)2 ]-(BF4 )4 in [D7 ]DMF revealed that the Pd8 chains were dissociated at higher temperature (T≈140 °C) into the Pd4 units of {Pd4 (μ-rac-dpmppm)2 }2+ and {Pd4 (μ-meso-dpmppm)2 }2+ , and they were thermodynamically self-aligned to restore the Pd8 chains at lower temperature (T<60 °C), through perfect chiral self-recognition between the stereogenic tetrapalladium units.

REVERSED TREND OF RADIAL DISTRIBUTION OF SUBPOPULATIONS IN THE GLOBULAR CLUSTERS NGC 362 AND NGC 6723

ABSTRACT Most globular clusters (GCs) are now known to host multiple stellar populations with different abundances of light elements. Here we use narrow-band photometry and low-resolution spectroscopy for NGC 362 and NGC 6723 to investigate their chemical properties and radial distributions of subpopulations. We confirm that NGC 362 and NGC 6723 are among the GCs with multiple populations showing bimodal CN distribution and CN–CH anticorrelation without a significant spread in calcium abundance. These two GCs show more centrally concentrated CN-weak, earlier generation stars compared to the CN-strong, later generation stars. These trends are reversed with respect to those found in previous studies for many other GCs. Our findings, therefore, seem contradictory to the current scenario for the formation of multiple stellar populations, but mass segregation acting on the two subpopulations might be a possible solution to explain this reversed radial trend.

Maintaining structural integrity of 4.5 V lithium cobalt oxide cathode with fumaronitrile as a novel electrolyte additive

Abstract The specific capacity of lithium-ion battery with lithium cobalt oxide as cathode depends on the upper limitation voltage for charge/discharge cycling, but this oxide tends to be destructed structurally when it is cycled in carbonate-based electrolyte under high voltage. We report a novel electrolyte additive, fumaronitrile (FN, CN CH CH CN), which can maintain the structural integrity of lithium cobalt oxide. Electrochemical measurements indicate that lithium cobalt oxide exhibits poor cyclic stability when it is cycled under 4.5 V (vs. Li/Li+) and the charged cathode suffers serious self-discharge in a base electrolyte, 1.0 mol L−1 LiPF6 in EC/EMC/DEC (3:5:2, by weight). These issues can be overcome effectively by adding 0.5% FN into the base electrolyte. Physical and chemical characterizations demonstrate that the poor cyclic stability and self-discharge of lithium cobalt oxide result from its structural destruction caused by HF formed from electrolyte decomposition, and FN yields a protective cathode interphase film which maintains the structural integrity of lithium cobalt oxide.

Reactivity of [M2 (μ-Cl)2 (cod)2 ] (M=Ir, Rh) and [Ru(Cl)2 (cod)(CH3 CN)2 ] with Na[H2 B(bt)2 ]: Formation of Agostic versus Borate Complexes.

Treatment of [M2 (μ-Cl)2 (cod)2 ] (M=Ir and Rh) with Na[H2 B(bt)2 ] (cod=1,5-cyclooctadiene and bt=2-mercaptobenzothiazolyl) at low temperature led to the formation of dimetallaheterocycles [(Mcod)2 (bt)2 ], 1 and 2 (1: M=Ir and 2: M=Rh) and a borate complex [Rh(cod){κ2 -S,S'-H2 B(bt)2 }], 3. Compounds 1 and 2 are structurally characterized metal analogues of 1,5-cyclooctadiene. Metal-metal bond distances of 3.6195(9) Å in 1 and 3.6749(9) Å in 2 are too long to consider as bonding. In an attempt to generate the Ru analogue of 1 and 2, that is [(Rucod)2 (bt)2 ], we have carried out the reaction of [Ru(Cl)2 (cod)(CH3 CN)2 ] with Na[H2 B(bt)2 ]. Interestingly, the reaction yielded agostic complexes [Ru(cod)L{κ3 -H,S,S'-H2 B(bt)2 }], 4 and 5 (4: L=Cl; 5: L=C7 H4 NS2 ). One of the key differences between 4 and 5 is the presence of different ancillary ligands at the metal center. The natural bond orbital (NBO) analysis of 1 and 2 shows that there is four lone pairs of electrons on each metal center with a significant amount of d character. Furthermore, the electronic structures and the bonding of these complexes have been established on the ground of quantum-chemical calculations. All of the new compounds were characterized by IR, 1 H, 11 B, 13 C NMR spectroscopy, and X-ray crystallographic analysis.

Non-Porous Iron(II)-Based Sensor: Crystallographic Insights into a Cycle of Colorful Guest-Induced Topotactic Transformations.

Materials capable of sensing volatile guests at room temperature by an easily monitored set of outputs are of great appeal for development as chemical sensors of small volatile organics and toxic gases. Herein the dinuclear iron(II) complex, [FeII2 (L)2 (CH3 CN)4 ](BF4 )4 ⋅2 CH3 CN (1) [L=4-(4-methylphenyl)-3-(3-pyridazinyl)-5-pyridyl-4H-1,2,4-triazole], is shown to undergo reversible single-crystal-to-single-crystal (SCSC) transformations upon exposure to vapors of different guests: 1 (MeCN)⇌2 (EtOH)→3 (H2 O)⇌1 (MeCN). Whilst 1 and 2 remain dimetallic, SCSC to 3 involves conversion to a 1D polymeric chain (due to a change in L bridging mode), which, remarkably, can undergo SCSC de-polymerization, reforming dimetallic 1. Additionally, SC-XRD studies of two ordered transient forms, 1TF3 and 2TF3, confirm that guest exchange occurs by diffusion of the new guests into the non-porous lattices as the old guests leave. These reversible SCSC events also induce color and magnetic responses. Indeed dark red 1 is spin crossover active (T1/2 ↓ 356 K; T1/2 ↑ 369 K), whilst orange 2 and yellow 3 remain high spin.

Syntheses and Structures of Xenon Trioxide Alkylnitrile Adducts.

The potent oxidizer and highly shock-sensitive binary noble-gas oxide XeO3 interacts with CH3 CN and CH3 CH2 CN to form O3 XeNCCH3 , O3 Xe(NCCH3 )2 , O3 XeNCCH2 CH3 , and O3 Xe(NCCH2 CH3 )2 . Their low-temperature single-crystal X-ray structures show that the xenon atoms are consistently coordinated to three donor atoms, which results in pseudo-octahedral environments around the xenon atoms. The adduct series provides the first examples of a neutral xenon oxide bound to nitrogen bases. Raman frequency shifts and Xe-N bond lengths are consistent with complex formation. Energy-minimized gas-phase geometries and vibrational frequencies were obtained for the model compounds O3 Xe(NCCH3 )n (n=1-3) and O3 Xe(NCCH3 )n ⋅[O3 Xe(NCCH3 )2 ]2 (n=1, 2). Natural bond orbital (NBO), quantum theory of atoms in molecules (QTAIM), electron localization function (ELF), and molecular electrostatic potential surface (MEPS) analyses were carried out to further probe the nature of the bonding in these adducts.

Synthesis and Characterization of [XeOXe](2+) in the Adduct-Cation Salt, [CH3 CN- - -XeOXe- - -NCCH3 ][AsF6 ]2.

Acetonitrile and [FXeOXe- - -FXeF][AsF6 ] react at -60 °C in anhydrous HF (aHF) to form the CH3 CN adduct of the previously unknown [XeOXe](2+) cation. The low-temperature X-ray structure of [CH3 CN- - -XeOXe- - -NCCH3 ][AsF6 ]2 exhibits a well-isolated adduct-cation that has among the shortest Xe-N distances obtained for an sp-hybridized nitrogen base adducted to xenon. The Raman spectrum was fully assigned by comparison with the calculated vibrational frequencies and with the aid of (18) O-enrichment studies. Natural bond orbital (NBO), atoms in molecules (AIM), electron localization function (ELF), and molecular electrostatic potential surface (MEPS) analyses show that the Xe-O bonds are semi-ionic whereas the Xe-N bonds may be described as strong electrostatic (σ-hole) interactions.

Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions.

Acetonitrile (CH3 CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH⋅⋅⋅N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp(2) and sp(3) bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst.