- The effect of fluorination in trimethylamine: gas-phase structures of CF3N(CH3)2 and (CF3)2NCH3
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The molecular structures of CF3N(CH3)2 and (CF3)2NCH3 have been determined by gas electron diffraction.The following skeletal parameters (ra distances and H=148.1(10) pm, N-CF=138.3(16) pm, CHNCH=113.0(27) o, CHNCF=111.9(9) o; (CF3)2NCH3:C-F=133.3(3) pm, N-CH=147.8(13) pm, N-CF=142.0(8) pm, CHNCF=116.8(13) o, CFNCF=117.8(11) o.CH and CF are the methyl and trifluoromethyl carbon atoms, respectively.Experimental uncertainties are 3? values and include possible systematic errors.The most surprising result is the large difference between the N-CH and N-CF bond lengths of about 10 and 6 pm in these compounds.All nitrogen bond angles increase concomitantly with increasing number of CF3 groups.An attempt is made to rationalize the observed structural trends.
- Jin, Anding,Zhu, Xiao-Lei,Kirchmeier, Robert L.,Shreeve, Jean'ne M.,Patel, Nimesh R.,Oberhammer, Heinz
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p. 129 - 134
(2007/10/02)
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- PERFLUOROALKYL DERIVATIVES OF NITROGEN. PART LI. REACTION OF THE N-HALOHENOBISTRIFLUOROMETHYLAMINES (CF3)2NX (X=Cl, Br) WITH NORBORNADIENE
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Reaction of the amines (CF3)2NX (X=Cl, Br) with norbornadiene either in solvent (CH2Cl2) at -78 deg C in the dark or in the vapour phase at 20 deg C in daylight gives a mixture of 3-halogeno-5-(NN-bistrifluoromethylamino)nortricyclene (exo, endo- and exo, exo-isomers) and exo-5-(NN-bistrifluoromethylamino)-anti-7-halogenonorbornene in quantitative yield formed via halonium ion addition to the diene.The reaction of the amine (CF3)2NBr in solvent Me2O or Et2O at -78 deg C in the dark gives the same products in low yield, together with 3-bromo-5-alkoxynortricyclene (exo, endo- and exo, exo-isomers) and the amine (CF3)2NR (R=Me, Et) in high yield.
- Haszeldine, R. N.,Tipping, A. E.,Valentine, R. H.
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p. 335 - 350
(2007/10/02)
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