Abstract
A review. The unusual bonding of boron in organoboranes or oligoboron clusters is not only apparent in diamagnetic mols. but also in paramagnetic systems, including mixed-valent species and oligoborane/carborane cluster radicals. The singly occupied MO of the radical ion C4B8R4H8.-, detd. by DFT calcns. Paramagnetic compds. with at least partially boron-centered electron spin can be constructed using either the prototypically electron-accepting boron atoms bridged by planar p-conjugated org. systems, or by taking advantage of the three-dimensional delocalized bonding in oligonuclear borane, haloborane, or carborane clusters. The concept of mixed valency can thus be transferred from org. and transition-metal chem. to main-group-element mols., and d. functional theory is capable of reproducing the variable spin distribution. on SciFinder(R)
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