Primary ethynamines (HC.tplbond.CNH2, PhC.tplbond.CNH2), aminopropadienone (H2NCH:C:C:O), and imidoylketene (HN:CHCH:C:O). Preparation and identification of molecules of cosmochemical interest

Wentrup, Curt; Briehl, Horst; Lorencak, P.; Vogelbacher, Uwe‐Josef; Winter, Hans; Maquestiau, A.; Flammang, Robert

doi:10.1021/ja00213a002

Cited by 66 publications

(27 citation statements)

References 5 publications

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“…0.0868 (5) N32 0.1819 (5) (4) 0.2301 (5) 0.1755 (5) 0.1461 (4) 0.3921 (4) 0.4033 (4) 0.3349 (4) 0.2811 (5) 0.2126 ( I ) 0.049 0.0897 (1) 0.052 0.1722 (3) 0.049 0.0193 (3) 0.040 -0.0028 (3) 0.039 0.1077 (4) 0.042 -0.0464 (4) 0.040 -0,0593 (4) 0.042 0.0326 (4) 0.042 0.2662 (5) 0.045 0.2906 (6) 0.067 0.3371 (7) 0.089 0.3592 (6) 0.084 0.3373 (6) 0.076 0.2908 (5) 0.067 -0.0936 (5) 0.050 -0.0589 (5) 0.053 0.0108 ( 5 ) 0.045 -0.1220 (5) 0.056 -0.1044 (5) 0.063 -0.0300 (5) 0.051 0.0481 (6) 0.055 0.1339 (5) 0.059 0.1694 (5) 0.052 -0.0519 (5) 0.052 (4) 0.4870 (6) 0.4717 (7) 0.03904 (2) 0.1422 (1) 0.0802 (2) -0.0606 (3) 0.1536 (4) -0.0207 (4) 0.0200 (4) (4) z l c 0.01802 (2) -0.0611 (2) 0.0536 (2) 0.1359 (5) 0.1243 (5) 0.0206 (5) -0.0790 (6) -0.0196 (7) 0.29404 …”

Section: Methodsunclassified

Multiple bonds between main-group elements and transition metals. 91. High-oxidation-state rhenium complexes containing the hydridotris(1-pyrazolyl)borato ligand

Degnan¹,

Behm²,

Cook³

et al. 1991

Inorg. Chem.

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2165Bulk Susceptibility Mmurements. The raw data (XRT = 3.58x 10-4 emu/mol) were corrected for temperature-independent diamagnetism (xd = -4.90 X lo4 emu/mo1)22 to afford the paramagnetic susceptibility xiT = 8.54 X lo-' emu/mol. This value is significantly larger than that of [Ni(tmp)12[Re04] (xi, Pt-spine conductors. The rhenium(VI1) complex [ H B ( p~)~l R e 0~ (1) is readily reduced by triphenylphosphine in the presence of excess (CH,)$iX (X = Br, Cl) to give the corresponding rhenium(V) complexes [HB(pz),]ReOX, (2, X = CI; 3, X = Br, pz = pyrazolyl (ClH1N2)).[HB(pz),]ReOCI2 (2), which seems to exist as two bond stretch isomers, reacts with 1 equiv of thiophenol in refluxing THF In the presence of a base [DBU or N(C,H,)J to give [HB(pz),]ReO(CI)(SC,H,) (4). Two equivalents of thiophenol reacts with 2 in refluxing THF, also in the presence of base, to give [ H B (~Z ) , ] R~O ( S C~H~)~ (5). 2 will react with 1.2-ethanedithiol or 1,2-benzenedithiol under similar conditions to give [HB(pz)l]ReO(S2C,H4) (6) and [HB(pz),]ReO(S2C2H4) (7), respectively. The solid-state structures of 4 and 5 have been determined by X-ray crystallography. Both were found to be monomeric with an approximately octahedral arrangement of ligands around the rhenium atoms. 4 crystallizes in the orthorhombic space group Pbcu (No. 61) with cell parameters a = 13.159 ( I ) A, b = 18.656 ( I ) A, c = 15.902 ( I ) A, V = 3904 ( I ) AI, Z = 8, R = 0.043, and R, = 0.031 for 271 3 reflections with I > 244). 5 crystallizes in the monoclinic space group P2Jc (No. 14) with cell parameters a = 15.594 (3) A, b = 21.624 (1) A, c = 15.931 (1) A, @ = 107.00 (I)', V = 5137 (1) AI, Z = 4, R = 0.050, and R, = 0.036 for 6683 reflections with I > 2 4 .

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Section: Methodsunclassified

Multiple bonds between main-group elements and transition metals. 91. High-oxidation-state rhenium complexes containing the hydridotris(1-pyrazolyl)borato ligand

Degnan¹,

Behm²,

Cook³

et al. 1991

Inorg. Chem.

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“…Compounds with the cyano-ynamine Scheme 2 Scheme 3 structure are known [27], but they might be expected to be thermally unstable. Although various ynamines have been generated under FVP conditions, and those with an NH present undergo isomerization to ketenimines [28,29], it appears that the presence of a CN group changes this reactivity in favor of radical fragmentation to give aniline as the only isolable product.…”

Section: Analysis Of Pyrolysatesmentioning

confidence: 99%

Synthesis, thermal reactivity, and kinetics of stabilized phosphorus ylides, part 2: [(Arylcarbamoyl)(cyano)methylene]triphenylphosphoranes and their thiocarbamoyl analogues

Aitken

Al‐Awadi

El‐Dusouqui

et al. 2006

Int J of Chemical Kinetics

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A series of five cyano(arylcarbamoyl) phosphorus ylides 2 and five cyano-(arylthiocarbamoyl) phosphorus ylides 3 are prepared and fully characterized. Pyrolytic reaction products of a representative example of each type obtained by flash vacuum pyrolysis technique show that they undergo thermal extrusion of Ph 3 PO or Ph 3 PS. Kinetic study of the gas-phase pyrolysis of each ylide by static method shows that these reactions are unimolecular and first order with no significant substituent effect, but the thiocarbamoyl ylides 3 react 40-65 times more rapidly than their carbamoyl analogues 2.

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“…The tautomerization of HNC to HCN will also be facilitated by collisions with the walls of the pyrolysis tube in FVT experiments. For the same reason all our attempts to observe the millimeterwave spectrum of some other unstable and easily tautomerizable molecules such as HOCN and H 2 N-C C-H failed because of wall-catalyzed isomerization to HNCO and HN¼C¼CH 2 /CH 3 CN, [32] respectively.…”

Section: Introductionmentioning

confidence: 99%

Chemical Activation in Azide and Nitrene Chemistry: Methyl Azide, Phenyl Azide, Naphthyl Azides, Pyridyl Azides, Benzotriazoles, and Triazolopyridines

Wentrup¹

2013

Aust. J. Chem.

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Chemical activation (the formation of 'hot' molecules due to chemical reactions) is ubiquitous in flash vacuum thermolysis (FVT) reactions, and awareness of this phenomenon is indispensable when designing synthetically useful gas-phase reactions. Chemical activation is particularly prevalent in azide chemistry because the interesting singlet nitrenes are high-energy intermediates, and their reactions are highly exothermic. Consequently, chemical activation is observed in the isomerization of methylnitrene CH 3 N to methylenimine (methanimine) CH 2 ¼NH, facilitating the elimination of hydrogen to form HCN or HNC. Rearrangements of phenylnitrene, 1-and 2-naphthylnitrenes, and 2-, 3-and 4-pyridylnitrenes afford cyanocyclopentadiene, 3-and 2-cyanoindenes, and 2-and 3-cyanopyrroles, all showing the effects of chemical activation by undergoing facile interconversion of isomers. Chemical activation can often be reduced or removed entirely by increasing the pressure, thereby promoting collisional deactivation. Larger molecules having more degrees of freedom are better able to dissipate excess energy; therefore the effects of chemical activation are less pronounced or completely absent in the formation of 3-cyanoindole and 1-cyanobenzimidazoles from 3-and 4-quinolylnitrenes and 4-quinazolinylnitrenes, respectively. In compounds possessing nitro groups, chemical activation can cause the loss of the nitro group at nominal temperatures far below those normally needed to cleave the C-NO 2 bond.

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Primary ethynamines (HC.tplbond.CNH2, PhC.tplbond.CNH2), aminopropadienone (H2NCH:C:C:O), and imidoylketene (HN:CHCH:C:O). Preparation and identification of molecules of cosmochemical interest

Cited by 66 publications

References 5 publications

Multiple bonds between main-group elements and transition metals. 91. High-oxidation-state rhenium complexes containing the hydridotris(1-pyrazolyl)borato ligand

Multiple bonds between main-group elements and transition metals. 91. High-oxidation-state rhenium complexes containing the hydridotris(1-pyrazolyl)borato ligand

Synthesis, thermal reactivity, and kinetics of stabilized phosphorus ylides, part 2: [(Arylcarbamoyl)(cyano)methylene]triphenylphosphoranes and their thiocarbamoyl analogues

Chemical Activation in Azide and Nitrene Chemistry: Methyl Azide, Phenyl Azide, Naphthyl Azides, Pyridyl Azides, Benzotriazoles, and Triazolopyridines

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