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The molecular structure of trimethylamine–borane (CH3)3N·BH3 has been determined from gas electron-diffraction data with spectroscopic data. The molecular parameter values and their uncertainties are rg(B–H)=1.261±0.006 Å, rg(N–B)=1.656±0.002 Å, rg(C–N)=1.485±0.001 Å, rg(C–H)=1.108±0.002 Å, ∠HBH=112.8±0.4°, and ∠CNC=109.2±0.2°. The potential barrier around the N–B bond has been estimated to be larger than 5 kcal mol−1 (1 cal=4.183 J). The isotope effects on the B–D bond distance and the DBD angle have also been estimated to be −0.006 Å and 0.4°, respectively, in rα0 parameters.

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