330474-31-2Relevant articles and documents
Mechanistic features of boron-iodine bond activation of B-iodocarboranes
Marshall, William J.,Young Jr., Robert J.,Grushin, Vladimir V.
, p. 523 - 533 (2001)
Oxidative addition of the B-I bond of 9-iodo-m-carborane to [(Ph3P)nPd] (n = 3, 4) is reversible, the equilibrium being shifted to the Pd(0) and the iodocarborane. In the presence of [(Ph3P)4Pd] and [Bu4N]Br in THF, 9-iodo-m-carborane undergoes halide exchange to produce 9-bromo-m-carborane. Coordinatively unsaturated Pd(0) and hydrido Pd(II) species generated upon thermal decomposition of [(Ph3P)2Pd(Ph)(O2CH)] and [(Ph3P)2Pd2(Ph)2 (μ-O2CH)2] reduce 9-iodo-m-carborane to m-carborane with 100% selectivity. The thermal decomposition of [(Ph3P)2Pd2(Ph)2 (μ-O2CH)2] in the presence of excess 9-iodo-m-carborane and PhI (1:1) results in the formation of m-carborane (3%) and [(Ph3P)2Pd2(Ph)2 (μ-I)2] (97%), whose structure was confirmed by single-crystal X-ray diffraction. X-ray analysis of 9-iodo-m-carborane and m-carboran-9-yl(phenyl)iodonium tetrafluoroborate shows that in the iodonium salt the B-I bond is longer by ca. 0.03 A? than in the iodocarborane. In contrast, the C-I bond distances in carboran-9-yl(phenyl)iodonium tetrafluoroborate (2.111(2) A?) and in iodobenzene (2.098(4) A?) are only marginally different. The elongation of the B-I bond, not the C-I bond, likely contributes to (i) the enhanced reactivity of B-carboranyl(phenyl)-iodonium cations toward nucleophiles and (ii) the remarkably high selectivity of these SN reactions that occur exclusively at the boron atom. A new crystallographic form of 9,10-diiodo-m-carborane is reported.