By Russell N. Grimes

ISBN-10: 012374170X

ISBN-13: 9780123741707

Carboranes moment variation is designed as a finished resource of knowledge in a box that has skilled huge, immense progress in either its primary and utilized features within the 4 a long time because the e-book of Carboranes (1970). in this lengthy interval millions of unique examine papers have seemed, in addition to many evaluation articles and ebook chapters facing points of carborane chemistry. As carborane technology has grown in complexity, and functions have complex gradually in components resembling drugs, nanostructured and electroactive fabrics, catalysis, polymers, and others, the necessity for a monograph protecting the whole region in a unified remedy has turn into more and more obvious. This quantity has critical targets, the 1st of that is 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 appropriate for readers in and academe who're now not proficient in boron chemistry yet locate themselves operating with, or lecturing approximately carboranes. Secondly, the e-book furnishes a trove of special details for staff energetic in carborane technology and linked applied sciences. accordingly, it contains tables directory hundreds of thousands of particular compounds keyed to literature references (supplemented through more information to be had on a website), including greater than 2,000 molecular constitution drawings that remove darkness from the accompanying dialogue. Thorough therapy of the synthesis, constructions, and reactions of carboranes, heterocarboranes, and metallacarboranes within the first thirteen chapters is by way of 4 chapters detailing advances in useful purposes in polymer technological know-how, catalysis, medication, and different parts. over 2,000 molecular constitution drawings light up 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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A much older idea is the use of carboranes as face-bound ligands in metal-carborane sandwich complexes (metalla­ carboranes), first demonstrated by Hawthorne in 1965. It has long been recognized that dicarbollide (C2B9H112À) and other carborane ligands are electronically related to cyclopentadieneide (C5RÀ 5 ), and complexes such as Ni(C2B9H11)2 and CpCo(C2B3H7) are analogues of metallocenes. Cyclic planar C2B3 and C3B2 carborane ligands are not only elec­ tronic but also steric analogues of C5H5À, and readily form stable multidecker and polydecker sandwiches via complex­ ation to metal centers on both faces (in contrast, few isolable C5R5-bridged metal sandwiches are known).

No other hypho-CB5 clusters are known at this time. 3 Nido-2,3-C2B4H8 Nido-2,3-dicarbahexaborane(8) (Figure 1-3, top right) and its derivatives, discovered by Onak, Williams, and their coworkers in 1962 [139,140], are the preparative starting point for a large area of metal sandwich chemistry involving 6- and 7-vertex nido-MC2B3, closo-MC2B4, and closo-M2C2B3 clusters and related systems, hundreds of which have been prepared and characterized (Chapter 13); among metallacarboranes, only the 12-vertex icosahedral complexes are more numerous.

The parent compound is generated together with other carborane products in the flow pyrolysis of 1-MeB5H8 or 1,2-Me2B5H7 [123]; when 1-ethylpentaborane is used as the reactant, nido-2-MeCB5H8 is obtained, together with methyl derivatives of 42 CHAPTER 4 Small carboranes: Four- to six-vertex clusters other carboranes. Flash thermolysis of 2-[(ClMe2Si)CH2]B5H8 affords 2-CB5H9 and closo-CB5H7 [124]. In a very different procedure, degradation of closo-1,6-C2B6H8 with BH4À salts, followed by treatment with anhydrous HCl, affords 2-CB5H9, along with several of its methyl, dimethyl, and trimethyl derivatives [125].

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Carboranes, Second Edition by Russell N. Grimes


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