Boron Nitrogen Compounds

Although the chemistry of boron is still relatively young, it is developing at a pace where even specific areas of research are difficult to compile into a monograph. Besides the boron hydrides, boron-nitrogen compounds are among the most fascinating derivatives of boron. Nitrogen compounds exist in a wide variety of molecular structures and display many interesting properties. The combination of nitrogen and boron, however, has some unusual features that are hard to match in any other combination of elements. This situation was first recognized by ALFRED STOCK and it seems proper to pay tribute to his outstanding work in the area of boron chemistry. One should realize that about forty years ago, STOCK and his coworkers had to develop completely new experimental techniq'\les and that no guidance for the interpreta tion of their rather unusual data had been advanced by theoretical chemists. In this monograph an attempt has been made to explore the general characteristics of structure and the principles involved in the preparation and reactions of boron-nitroge~ compounds. It was a somewhat difficult task to select that information which appears to be of the most interest to "inorganic and general chemistry" since the electronic relationship between a boron-nitrogen and a carbon-carbon grouping is reflected in the "organic" character of many of the reactions and compounds.

The present issue, Volume 3a of "Boron Compounds" 4th Supplement of the Gmelin Hand book, presents the description of boron nitride and a part of other boron compounds containing nitrogen. Volume 3 b (to be published Later) will complete the presentation of the boron-nitrogen compounds and will also cover boron compounds containing fluorine. Due to technical circumstances, Volume 1 (systems with hydrogen) and Volume 2 (systems with oxygen) of this particular supplement will be published subsequently, whereas Volume 4 (boron compounds containing CL, Br, I, S, Se, and Te, as well as a section containing carboranes) has already been published. ALL volumes of the 4th Supplement will be augmented by a formula index. The IUPAC nomenclature is generally adhered to; occasional abbreviations for compounds are explained in the text. A positive sign for the chemical shifts of the NMR signals indicates a 1 13 downfield shift from the references, usually internal (CH ) Si for 6 H and 6 C and external 3 4 11 (C H h0-BF for 6 B, others being specified. 2 5 3 In contrast to more recent publications but remaining consistent with the previous volumes of the Boron Series, the iminoborane structure is written as B=N and not as B=N. In fact, the real electronic structure is more realistically symbolized by B=N, but it seems reasonable to avoid =NR in accordance with the commonly accepted "iminoborane" nomenclature.

The present issue, Volume 3a of "Boron Compounds" 4th Supplement of the Gmelin Hand book, presents the description of boron nitride and a part of other boron compounds containing nitrogen. Volume 3 b (to be published Later) will complete the presentation of the boron-nitrogen compounds and will also cover boron compounds containing fluorine. Due to technical circumstances, Volume 1 (systems with hydrogen) and Volume 2 (systems with oxygen) of this particular supplement will be published subsequently, whereas Volume 4 (boron compounds containing CL, Br, I, S, Se, and Te, as well as a section containing carboranes) has already been published. ALL volumes of the 4th Supplement will be augmented by a formula index. The IUPAC nomenclature is generally adhered to; occasional abbreviations for compounds are explained in the text. A positive sign for the chemical shifts of the NMR signals indicates a 1 13 downfield shift from the references, usually internal (CH ) Si for 6 H and 6 C and external 3 4 11 (C H h0-BF for 6 B, others being specified. 2 5 3 In contrast to more recent publications but remaining consistent with the previous volumes of the Boron Series, the iminoborane structure is written as B=N and not as B=N. In fact, the real electronic structure is more realistically symbolized by B=N, but it seems reasonable to avoid =NR in accordance with the commonly accepted "iminoborane" nomenclature.

The volume presents compounds of boron with nitrogen and with fluorine and updates the preceding supplement series. The majority of the boron-nitrogen compounds includes amine-boranes (more than 250 compounds), pyrazaboles, and nitrogen-substituted boron cations. Emphasis is placed also on ammonium borates and on three- and four-coordinate boron-nitrogen compounds containing B-O bonds. In the fluorine part, special attention was given to BF3 and to the tetrafluoroborates. As many as 500 recent publications on applications of BF3 and its etherate have been evaluated. Ions, radicals, and neutral compounds containing only B, F, and partly also H or O are discussed. Moreover, linear and cyclic organylfluoroboranes and aminofluoroboranes and their adducts are treated. Peroxy species are found among the OxBFy-group compounds with four-coordinate boron.