Water adducts of BX(3) and CX(3)(+): implications for structure, bonding, and reactivity

Good quality ab initio calculations (MP2) show that the water adducts of BX(3) and CX(3)(+) have totally different structures (X = F-I). While all H(2)O-BX(3) complexes have classical C(s) symmetric structures with strong B-O bonds and additional H-bonding, the heavier CX(3)(+) cations (X = Cl-I) form weakly bonded "non-classical" water adducts that maximize C-X pi-bonding rather than C-O sigma-bonding. The delocalization of the positive charge as the driving force for pi-bond formation is absent in BX(3), and therefore, pi-bonding is only weak and not structure determining in H(2)O-BX(3). Since the PES of all H(2)O --> EX(3)(0/+1) particles (E = B, C) is very flat, flexible basis sets (like TZVPP) are required to rigorously characterize the adducts. In earlier calculations (J. Am. Chem. Soc. 1997, 119, 6648), classical structures were reported for all H(2)O --> EX(3)(0/+1) (E = B, C) complexes, likely resulting from the insufficient quality of the basis sets employed. By introducing a positive charge to three coordinate boron-halogen cations Do --> BX(2)(+) (Do = NH(3), OH(2), X-H), also the B-X bonds shrink due to the stronger pi-bonding induced by the positive charge delocalization and if compared to the respective neutral compounds like H(2)N-BX(2) or BX(3). The "non-classical" water adducts also suggest that the mechanism of organic reactions involving carbenium ion intermediates with alpha-bromine or -iodine substituents and a nucleophile may proceed through halogen- rather than carbon coordination.