caa a22 4500 477139418 CHVBK 20180405111728.0 cr unu---uuuuu 170330e19970401xx s 000 0 eng 10.1007/BF02767676 doi (NATIONALLICENCE)springer-10.1007/BF02767676 The kinetics of reaction of 4-nitrophenylnitromethane with N'-Propyl-N,N-dipropylbenzimidamide in aprotic solvents. a steric effect on tunneling [Elektronische Daten] [Naja Ellis, Colin Hubbard] Thermodynamic and kinetic parameters have been established for the reaction between the carbon acid, 4-nitrophenylnitromethane, (4-NPNM), and the base N'-n-propyl-N,N-di-n-propylbenzimidamide, (N'PDPBA), in mesitylene and in chlorobenzene. In some cases deuteron transfer from 4-(D2)NPNM to the base has also been studied. In addition, some results for the proton transfer reaction in tetrahydrofuran have been collected. Spectrophotometric methods have been employed to monitor the ion-pair product, which is solvatochromic. In general the solvent dependence of the parameters is as expected, but there is some indication of specific solvation. The kinetic isotope effects of 11 and 8 in mesitylene and chlorobenzene, respectively, are larger than those predicted classically. However, as is discussed the n-propyl group on the secondary nitrogen of the base may serve to reduce the extent of tunneling compared to that in an unsubstituted analogue by a steric effect. Plenum Publishing Corporation, 1997 Carbon acid-base reaction nationallicence kinetics nationallicence isotope effects nationallicence tunneling nationallicence steric effect nationallicence Ellis Naja Department of Chemistry, University of New Hampshire, 03824-3598, Durnham, New Hampshire aut Hubbard Colin Department of Chemistry, University of New Hampshire, 03824-3598, Durnham, New Hampshire aut Journal of Solution Chemistry Springer US 26/4(1997-04-01), 369-378 0095-9782 26:4<369 1997 26 10953 https://doi.org/10.1007/BF02767676 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF02767676 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Ellis Naja Department of Chemistry, University of New Hampshire, 03824-3598, Durnham, New Hampshire aut NATIONALLICENCE 700 1- Hubbard Colin Department of Chemistry, University of New Hampshire, 03824-3598, Durnham, New Hampshire aut NATIONALLICENCE 773 0- Journal of Solution Chemistry Springer US 26/4(1997-04-01), 369-378 0095-9782 26:4<369 1997 26 10953 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer