32488-48-5Relevant academic research and scientific papers
Efficient synthesis of diphenylketene-13C2
Anderson,Broughton
, p. 2379 - 2380 (2001)
A short and efficient synthesis of doubly 13C labeled diphenylketene from relatively cheap 13C labeled carbon dioxide, as the sole source of labeled carbon, is described in 22% overall yield.
Bimodal Fluorescence/Magnetic Resonance Molecular Probes with Extended Spin Lifetimes
Yang, Shengjun,Saul, Philip,Mamone, Salvatore,Kaltschnee, Lukas,Gl?ggler, Stefan
, (2022/01/11)
Bimodal molecular probes combining nuclear magnetic resonance (NMR) and fluorescence have been widely studied in basic science, as well as clinical research. The investigation of spin phenomena holds promise to broaden the scope of available probes allowi
Coordination behaviors of diphenylketene adsorbed in the nanocages of zeolite NaY and AgY
Shibata, Shintaro,Masui, Yoichi,Onaka, Makoto
, p. 663 - 670 (2020/12/29)
We investigated in detail how polar cumulene molecules like diphenylketene were accommodated in faujasite zeolite pores based on 13C CP/MAS and DD/MAS NMR analyses as well as quantum chemical calculations after adsorbing the molecule into the zeolite NaY or AgY having “hard” sodium ions or “soft” silver ions. Since the diphenylketene has such a specific structure that a carbonyl group (a hard base) is accumulated by a carbon-carbon double bond (a soft π base), which is conjugated with two benzene rings (soft π bases), it is possible for the diphenylketene to adopt multicoordination modes to different metal ions in the zeolite. Compared with the coordination modes of benzophenone and 1,1-diphenylethene adsorbed in the NaY and AgY, those of diphenylketene were identified, and specific coordination behaviors in the zeolite’s supercages were classified depending on the hard or soft metal characters: The C=O and phenyl coordination modes to Na+ in NaY prevail, while the C=C and phenyl coordination to Ag+ in AgY is favored. We also unveiled the difference in the molecular mobility depending on the types of cations in the zeolite by comparing the 13C CP/MAS and DD/MAS NMR spectra.
Isomerization polymerization of the phosphaalkene MesP=CPh2: An alternative microstructure for poly(methylenephosphine)s
Siu, Paul W.,Serin, Spencer C.,Krummenacher, Ivo,Hey, Thomas W.,Gates, Derek P.
supporting information, p. 6967 - 6970 (2013/07/26)
Unique pathway: The radical-initiated addition polymerization of MesP=CPh2 propagates through the ortho-bound CH3 group of the Mes moiety after C-H bond activation (see scheme, Mes=2,4,6-trimethylphenyl, tht=tetrahydrothiophene, TEMPO=2,2,6,6-tetramethyl-l-piperidinoxyl). This unique isomerization polymerization mechanism contrasts the previously suggested head-to-tail enchainment typically observed for olefins. Copyright
Synthesis of [11C]/(13C)amines via carbonylation followed by reductive animation
Rahman, Obaidur,Kihlberg, Tor,Langstroem, Bengt
, p. 1612 - 1616 (2007/10/03)
Twelve 11C-labelled amines were prepared via 11C-carbonylation followed by reductive amination. The 11C-carbonylation was performed in the presence of tetrakis(triphenylphosphine)palladium using aryl iodides or aryl trifla
Free Energies of Electron Transfer from Ketyls to Isotopically Substituted Ketones
Stevenson, Cheryl D.,Halvorsen, Troy D.,Kage, David E.,Reiter, Richard C.,McElheny, Daniel J.
, p. 4634 - 4638 (2007/10/02)
A series of electron transfer competition reactions between several isotopically different benzophenones was established in liquid ammonia.The resulting electron transfer A(.-) + B = A + B(.-) equilibrium constants were determined via EPR studies and via the physical separation of the anion radical phase from the neutral molecule phase.This anion radical-neutral molecule separation leads to a partial separation of the isotopic isomers involved due to the deviation of the equilibrium constants from unity.Mass spectral analysis of the two phases yields thermodynamic data for the electron transfer that is consistent with the EPR results: when A = benzophenone, Keq at -75 deg C equals 0.52, 0.50, and 0.83 for equilibria involving B = perdeuteriated benzophenone, benzophenone, and benzophenone, respectively.
Altered Condensed-Phase Electron Affinities of Carbonyl- 13C-, 14C-, and 17O-Substituted Ketones
Lauricella, Toni L.,Pescatore, John A.,Reiter, Richard C.,Stevenson, Randal D.,Stevenson, Gerald R.
, p. 3687 - 3691 (2007/10/02)
Electron spin resonance experiments have shown that the solution electron affinities of both benzoquinone (BQ) and benzophenone (BZO) in liquid ammonia are diminished when a 13C replaces the 12C in the carbonyl position.For the reaction *R+R.-=*R.-+R, where *R represents the 13C-substituted material (either BZO-13C or BQ-13C), the equilibrium constants (Keq) are 0.80 and 0.50 at -75 deg C for the BQ and BZO systems, respectively.The reduction of radioactive samples of benzophenone (mixtures of BZO and BZO-14C, 14C substitution at the carbonyl carbon) with deficient amounts of sodium metal in liquid ammonia followed by removal of the ammonia leaves a solid mixture of benzophenone and benzophenone ketyl.Sublimation of the neutral benzophenone from the anion radical salt produces benzophenone that is enhanced in radioactivity relative to the starting BZO/BZO-14C mixture.This enhancement in radioactivity is consistent with the equilibrium constant again being less than unity when *R represents the 14C-substituted benzophenone.In contrast to these results, substitution of the oxygen atom with 17O results in an increase in the relative solution electron affinity.This is explained in terms of the increase in "bonding" involving the oxygen upon reduction, due to ion association.
SYNTHESIS AND STRUCTURE OF ARYL-SUBSTITUTED PHOSPHA-ALKENES
Knaap, Th.A. van der,Klebach, Th.C.,Visser, F.,Bickelhaupt, F.,Ros, P.,et al.
, p. 765 - 776 (2007/10/02)
An improved synthesis of the two triarylsubstituted phospha-alkenes mesityl (diphenylmethylene)phosphine (1a) and 2,6-dimethylphenyl(diphenylmethylene)phosphine (1b) described.Of several variants, the preferred route starts with the aryl bromides 4 which
