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Extra resources for Aminomethylenemalonates and Their Use in Heterocyclic Synthesis
However, the predicted energy difference between the open and the bridged isomers of C2H3+ is calculated by the AIMD Page 22 TABLE 4. 45c Mode v (ab initio)v (corrected)av (ab initio)v (ab initio)v (corrected)av (ab initio)v (ab initio)vlinear C2H3+(1)CH1 stretch a1 3453317433603364317933173327CH2,3 s stretchb a1 3222293530953126295430433028C-C stretch a1 1813162217561753167017731783CH2,3 s ipbb a1 135412271219125411781161CH2,3 a stretchb b1 3322302631903217304031203103CCH1 ibpb b1 11661103110610851097CCH2,3 + CCH1 ipbb b1 481 208 345133i193iCCH2,3 s opbb b2 1034 904 830 873 808 815CCH1 opbb b2 661 643 601 625 686bridged C2H3+(2)C1,2H1,2 s stretchb a1 3541325534243443325433893403H3C1,2 stretch a1 25162467247123662385C-C stretch a1 2122189919222000190519261939CCH1,2 s ipbb a1 991 909 923 892 917CCH1,2 a opbb a2 734 586 554 587 523 617C1,2H1,2 a stretchb b 1 34243148332733393155329533043140CCH3 ipbb b1 13231333127913141315CCH1,2 a ipbb b1 379 657 513 645 696CCH1,2 s opbb b2 845 719 738 757 725 770aCorrected by an empirical factor, for details see ref.
Lodder 377 9. Synthetic Applications M. D. Schiavelli 433 10. Alkynyl and Aryl Cations P. J. Stang 451 Index 461 Page xi Contributors Y. ApeloigDepartment of Chemistry, Technion-Israel Institute of Technology, 32000 Haifa, IsraelD. H. AueDepartment of Chemistry, University of California, Santa Barbara, CA 93106, USAC. A. GrobInstitut für Organische Chemie der Universität, Basel 4056, SwitzerlandT. KitamuraDepartment of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, Hakozaki, Fukuoka 81281, JapanG.
This assignment was based on the spin statistical weight of the observed K=1, K-doublets for the rotational transitions, on the comparison of the observed rotational constants with calculated values21,23 and on the absence of other equally strong vibrational bands in the region between 3300 and 2700 cm1, which theory23 predicts for the classic vinyl cation 1. The experiment also reveals that the observed C2H3+ is highly fluxional, the three hydrogens exchanging their equilibrium positions. The resulting tunneling splitting is spectroscopically resolved for the rotational transitions in excited vibrational states45, as predicted by theoretical models51.
Aminomethylenemalonates and Their Use in Heterocyclic Synthesis by Alan R. Katritzky (Eds.)