Pr. Kemper et al., CLUSTER-ASSISTED THERMAL-ENERGY ACTIVATION OF THE H-H SIGMA-BOND IN H-2 BY GROUND-STATE B-1(0)) IONS - OVERCOMING A 77 KCAL((S)MOL BARRIER/, Journal of the American Chemical Society, 120(30), 1998, pp. 7577-7584
Binding energies for the sequential addition of two dihydrogen ligands
to ground-state B+(S-1(0)) ions have been measured with use of equili
brium methods. The dissociation energies at 0 K were determined to be
3.8 and 3.0 kcal/mol, respectively. Similar measurements on inserted H
BH+(1 Sigma(g)(+) ground state) ions yielded binding energies of 14.7
and 18.0 kcal/mol for the addition of the first two Hz ligands. Inject
ion of B+ into a cell containing 5 Torr of H-2 near 100 K resulted in
a BH6+ terminal ion that was not in equilibrium with the lower mass B, B+(H-2), and B+(H-2)(2) species. The rate constant for;formation of
this BH6+ terminal ion was measured as a function of temperature and f
ound to peak near 100 K, rapidly decreasing at higher and lower temper
atures. This highly unusual behavior was successfully quantitatively m
odeled by assuming;he following mechanism, B+ + 3H(2) F reversible arr
ow B+(H-2)(3) -->(o) HBH(H-2)(2)(+), where the third uninserted cluste
r could rearrange with a 0.52 +/- 0.5 kcal/mol barrier to form the muc
h lower energy inserted ion. ;High-level ab initio calculations (ref 1
7) found a barrier of 77 kcal/mol for this-insertion process when grou
nd-state B+ reacts with a single H2 molecule. Our experiments show tha
t addition of two weakly bound H-2 ligands reduces the barrier to near
zero. To confirm this result, large basis set DFT calculations were d
one to explore the reaction pathway. These calculations do, in fact, p
redict a near-zero barrier for insertion upon adding a third H-2 to gr
ound-state Bf(H2)2 ions. This DFT result has recently been confirmed b
y high-level ab initio calculations published elsewhere (refs 29 and 3
0). Additional high-level ab initio calculations on the Bf(H2)2 cluste
rs are reported here and provide quantitative agreement with the measu
red bond energies.