52089-62-0Relevant academic research and scientific papers
Infrared Intensities: Cyclobutene. A Normal-Coordinate Analysis and Comparison with Cyclopropene
Wiberg, Kenneth B.,Rosenberg, Robert E.
, p. 8282 - 8292 (1992)
The infrared and Raman spectra of cyclobutene and of its 1,2-d2 and 3,3,4,4-d4 isotopomers were determined, and the intensities of the infrared bands were measured.A new vibrational assignment was made with the help of the spectrum calculated using the 6-31G* basis set.A normal-coordinate analysis was carried out, and the infrared intensities were converted to atomic polar tensors and to dipole moment derivatives with respect to symmetry coordinates.The results of this investigation are compared with similar data obtained previously for cyclopropene and with corresponding data for cyclopropane, ethylene, and propane.
Reduction of Activated Alkenes by PIII/PV Redox Cycling Catalysis
Longwitz, Lars,Werner, Thomas
supporting information, p. 2760 - 2763 (2020/02/05)
The carbon–carbon double bond of unsaturated carbonyl compounds was readily reduced by using a phosphetane oxide catalyst in the presence of a simple organosilane as the terminal reductant and water as the hydrogen source. Quantitative hydrogenation was observed when 1.0 mol % of a methyl-substituted phosphetane oxide was employed as the catalyst. The procedure is highly selective towards activated double bonds, tolerating a variety of functional groups that are usually prone to reduction. In total, 25 alkenes and two alkynes were hydrogenated to the corresponding alkanes in excellent yields of up to 99 %. Notably, less active poly(methylhydrosiloxane) could also be utilized as the terminal reductant. Mechanistic investigations revealed the phosphane as the catalyst resting state and a protonation/deprotonation sequence as the crucial step in the catalytic cycle.
Stainless-Steel Ball-Milling Method for Hydro-/Deutero-genation using H2O/D2O as a Hydrogen/Deuterium Source
Sawama, Yoshinari,Kawajiri, Takahiro,Niikawa, Miki,Goto, Ryota,Yabe, Yuki,Takahashi, Tohru,Marumoto, Takahisa,Itoh, Miki,Kimura, Yuuichi,Monguchi, Yasunari,Kondo, Shin-Ichi,Sajiki, Hironao
, p. 3773 - 3776 (2015/12/08)
A one-pot continuous-flow method for hydrogen (deuterium) generation and subsequent hydrogenation (deuterogenation) was developed using a stainless-steel (SUS304)-mediated ball-milling approach. SUS304, especially zero-valent Cr and Ni as constituents of the SUS304, and mechanochemical processing played crucial roles in the development of the reactions.
Facile and convenient method of deuterium gas generation using a Pd/C-catalyzed H2-D2 exchange reaction and itsapplication to synthesis of deuterium-labeled compounds
Kurita, Takanori,Aoki, Fumiyo,Mizumoto, Takuto,Maejima, Toshihide,Esaki, Hiroyoshi,Maegawa, Tomohiro,Monguchi, Yasunari,Sajiki, Hironao
scheme or table, p. 3371 - 3379 (2009/04/10)
The Pd/C-catalyzed H2-D2 exchange reaction using a H2-D2O combination provided a general, efficient and environmentally friendly route for the preparation of deuterium gas (D 2). H2 sealed
Complete replacement of H2 by D2 via Pd/C-catalyzed H/D exchange reaction
Sajiki, Hironao,Kurita, Takanori,Esaki, Hiroyoshi,Aoki, Fumiyo,Maegawa, Tomohiro,Hirota, Kosaku
, p. 3521 - 3523 (2007/10/03)
(Chemical Equation Presented) A general and in situ D2 gas generation method using 10% Pd/C-catalyzed H2-D2 exchange reaction in a H2-D2O system has been developed. H 2 gas sealed in a reac
Structure of the radical cations of N,N'-polymethylene-synl, 1, 6:8, 13-diimino[14]annulenes: An ESR and ENDOR study
Gerson, Fabian,Gescheidt, Georg,Kn?bel, Jürgen,Martin Jr., William B.,Neumann, Ludger,Vogel, Emanuel
, p. 7107 - 7115 (2007/10/02)
N,N'-Polymethylene-syn-1,6:8,13-diimino[14]annulenes, 1-7, in which the number, m, of CH2 groups varies from 1 to 7, and N,N'-dimethyl-syn-1,6:8,13-diimino[14]annulene (8) were synthesized. The radical cations of 1-8, as well as those of several derivatives of 1-4, have been studied by ESR, ENDOR, and TRIPLE resonance spectroscopy. In contrast to the corresponding anions 1*--8*-, which are bridged π-perimeter radicals, the cations 1*+-8*+ must be considered as N-centered radicals with the bulk of the spin population residing at the two heteroatoms. The structure and properties of these radical cations critically depend on the length of the polymethytene chain linking the N atoms. When the number, m, of the CH2 groups in this chain is 1 or 2, the N lone pairs are directed "outward", so that their interaction is relatively weak. Thus, the radical cations 1*+ (m = 1) and 2*+ (m = 2) are thermodynamically and kinetically rather unstable, and their 14N coupling constant, aN, is only 0.6-0.7 mT. on the other hand, with m = 3-7 the N lone pairs point "inward", an arrangement that favors the formation of an N-N three-electron σ-bond. The pertinent radical cations 3*+-7*+ (m = 3-7) exhibit unusual thermodynamic and kinetic stabilities which, in two (3*+ and 4*+), allowed X-ray crystallographic structure analyses to be carried out. The coupling constant aN amounts to 1.70 to for 3*+, it increases further to an almost constant value of 2.57-2.72 mT for 4*+-7*+; an aN value of 2.66 mT is also observed for 8*+, which may be regarded as having its N atoms linked by a very long polymethylene chain. The changes in the coupling constant aN along the 1*+-7*+ (8*+) series can be rationalized in terms of the varying "s-character" of the singly occupied orbital centered at the spin-bearing N atoms.
