Carboranes, Second Edition by Russell N. Grimes

By Russell N. Grimes

Carboranes moment variation is designed as a finished resource of data in a box that has skilled huge, immense development in either its primary and utilized facets within the 4 a long time because the ebook of Carboranes (1970). in this lengthy interval millions of unique learn papers have seemed, besides many assessment articles and booklet chapters facing points of carborane chemistry. As carborane technological know-how has grown in complexity, and functions have complicated progressively in parts corresponding to medication, nanostructured and electroactive fabrics, catalysis, polymers, and others, the necessity for a monograph overlaying the complete sector in a unified therapy has develop into more and more obvious. This quantity has important goals, the 1st of that's to supply a readable and concise advent to the fundamental ideas underlying the synthesis, buildings, reactivity, and purposes of carboranes and metallacarboranes at a degree compatible for readers in and academe who're now not knowledgeable in boron chemistry yet locate themselves operating with, or lecturing approximately carboranes. Secondly, the e-book furnishes a trove of certain info for staff energetic in carborane technological know-how and linked applied sciences. hence, it contains tables directory hundreds of thousands of particular compounds keyed to literature references (supplemented through more information on hand on a website), including greater than 2,000 molecular constitution drawings that remove darkness from the accompanying dialogue. Thorough remedy of the synthesis, buildings, and reactions of carboranes, heterocarboranes, and metallacarboranes within the first thirteen chapters is through 4 chapters detailing advances in functional purposes in polymer technological know-how, catalysis, drugs, and different components. over 2,000 molecular constitution drawings remove darkness from the textual content all through tables directory millions of compounds with key literature references supplemental details at the book's web site

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Although somewhat more reactive than its higher congeners in the closo-C2BnÀ2Hn series, the parent carborane is unaffected by O2, H2O, NEt3, CO2, or acetone at room temperature [49]. However, unlike the larger closo-carboranes, liquid 1,5-C2B3H5 slowly polymerizes on standing, forming a dimer and higher molecular weight products [109]. A 1:1 adduct forms with NMe3 at low temperatures, but on melting it converts to an intractable polymer [109]. 2B Pyrolysis of 1,5-C2B3H5 has been investigated by several groups, who found that the main product is the B2 bonded dimer 2,20 -(1,5-C2B3H4)2 [109–111]; by trapping products on a cold finger in the reactor, higher oligomers including the B2 2B bonded trimer 2,20 -3,20 -(1,5-C2B3H4)2À1,5-C2B3H3 have been isolated and characterized [110,111].

The compound combines with NEt3 to form a stable 1:1 adduct, and exposure to a limited amount of bromine in solution or in the gas phase results in apparent addition to the cage C2 2C bond, 2C bond, but without release of H2 or HBr. At the time, this finding suggested [28] possible double-bond character for the C2 ˚ determined later from electron diffraction data [29]. 626 A attacks and destroys the carborane cage. Reaction with Fe(CO)5 under ultraviolet light [28] affords the nido-ferracarborane 1,2,3-(CO)3Fe(C2B3H7), a known [39,40] complex that contains a planar C2B3 ring ligand.

Ethylene combines with 1,2-C2B3H7 in the gas phase at 90  C to give tetraethyldiborane, triethylboron, and unidentified products [28]. Treatment with NaH in THF in an attempt at bridge-deprotonation to form the C2B3H6À ion results in decomposition, while exposure to NaH in mineral oil gives no reaction. Molecular orbital calculations on the experimentally unknown C2B3H52À dianion and its hypothesized cage rearrangement show open pyramidal geometry for the various possible isomers [41]. The reaction of 1,2-C2B3H7 with NH3 has been explored computationally and the C2B3H7ÁNH3 adduct is found to be less stable than the uncomplexed carborane [42].

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