Interaction of iron with boron in metal-rich metallaboranes resulting in large deshielding and rapid relaxation processes of the boron-11 nucleus

A first-order, parameterized model for calculating 11B chemical shifts in metal-rich ferraboranes and a correlation of chemical shift with boron Mulliken populations from Fenske-Hall calculations are presented. These correlations are qualitatively different from those reported earlier for boranes and suggest that direct iron-boron interactions lead to large deshielding due to substantial increases in multiple-bond contributions to the shielding tensor. Relaxation rates have been measured for [Fe4(CO)12BH/sub 3-n/]/sup n-/ (n = 0-2) and correlated with electric field gradients at the boron nucleus estimated from Fenske-Hall calculations. These results demonstrate that formation of the boride, [Fe4(CO)12B]3-, by deprotonation is accompanied by the development of large asymmetries in the electronic charge distribution around the boron nucleus. Finally, 7Li NMR is used to probe the nature of the anions [Fe4(CO)12BH/sub 3-n/]/sup n-/ (n = 1-3), and observed line shapes suggest close association of Li+ with the trianion. 28 references, 3 figures, 4 tables