RESUMO
New alkyl derivatives of the nido-dicarbapentaborane, 1,2-C(2)B(3)H(7), and arachno-carbapentaborane, 1-CB(4)H(10), have been identified as the main volatile carbaborane products in quenched gas-phase reactions of tetraborane(10), B(4)H(10), with alkyl-substituted ethynes RC[triple bond]CR' (R = Me, Et, (n)Pr or (t)Bu, R' = H; R = Me or Et, R' = Me). The gaseous mixtures were heated at 70 degrees C, and monitored by gas-phase mass spectrometry. Each reaction was quenched when the ethyne was used up. The quenched gas-phase reaction of B(4)H(10) and Me(3)SiC[triple bond]CH gave a single volatile carbaborane product, 1-Me(3)Si-1,2-C(2)B(3)H(6).
RESUMO
The molecular structure of nido-1,2-C(2)B(3)H(7), 1, the principal volatile carborane generated in the quenched gas-phase reaction of B(4)H(10) and ethyne at 70 degrees C, has been determined by a combined analysis of gas-phase electron-diffraction data and rotation constants restrained by ab initio computations at the CCSD(T)/TZP' level. The structure is consistent with a geometry having C(s)() symmetry, similar to that of pentaborane(9). The apical position is occupied by a carbon atom, displaced toward B(4) from a position directly above the B(5).B(3) vector, and hydrogen atoms asymmetrically bridge the B-B bonds. The basal atoms are almost coplanar, C(2) lying ca. 2 degrees below the B(3)-B(4)-B(5) plane. Important experimental structural parameters (r(alpha) degrees /pm, angle(alpha)/ degrees ) are r[C(1)-C(2)] = 162.6(6); r[C(1)-B(3)] = 161.4(3); r[C(2)-B(3)] = 154.3(2); r[C(1)-B(4)] = 157.4(5); r[B(3)-B(4)] = 185.7(3);
RESUMO
The molecular structure of trifluorophosphine tetraborane(8), B(4)H(8)PF(3), has been studied in the gas phase by electron diffraction. The experimental data can be fitted using a model which represents the gas as consisting solely of the endo conformer with C(s)() symmetry, the PF(3) group staggered with respect to the B(1)-H(1) bond. Important experimental structural parameters (r(alpha) degrees ) are r[B(1)-B(2)] (hinge-wing) = 184.7(9) pm, r[B(1)-B(3)] (hinge-hinge) = 172.2(12) pm, r[B(2)-B(3)] = 179.9(10) pm,r[B(1)-P] = 179.8(9) pm, and r(P-F) (mean) = 152.8(1) pm; B(3)B(1)P = 131.6(11) degrees, and the dihedral ("butterfly") angle between the planes B(1)B(2)B(3) and B(1)B(4)B(3) is 133.9(23) degrees. These values agree well with the ab initio (MP2/TZP level) optimized molecular geometry for the endo conformer; at the MP2/TZP//MP2/TZP + ZPE(HF/6-31G) level, the exo conformer is predicted to represent ca. 2% of the compound vapor, consistent with the experimental (11)B NMR solution spectrum. The experimental and theoretical geometries are supported by comparison of the calculated (IGLO) (11)B NMR chemical shifts with the experimental NMR data.
