For almost a quarter of a century the words "nuclear magnetic reso nance" were synonymous with proton I,leasurements. During this period the literature abounded with a seemingly infinite variety of 1H NHR studies concerned primarily with carbon chemistry. Occasionally a "novel" nucleus was studied and, even in those early days, the poten- 13 14 31 19 tial offered by C, N, P and F was clearly recognized. Despite the allure, the technical difficulties involved in measuring some of these nuclei were far from trivial. Small magnetic moments and low natural abundance in combination with spin-spin coupling from other nuclei, mostly protons, resulted in a signal-to-noise problem whose severity effectively excluded the study of metal complexes with unfa vorable solubility characteristics. The first important breakthrough came with the advent of broad band 1H-decoupling. For example, the featureless broad 31p resonance associated with the commonly used ligand triphenyl phosphine is converted to a sharp, more readily ob served singlet when wide-band decoupling is employed (see Fig. 1). Despite this improvement investigation of more interesting molecules, such as catalytically active complexes was forced to await the devel opment of Fourier Transform methods since only with relatively rapid signal averaging methods could sufficient signal-to-noise ratios be achieved.

Although it was shown very early [1] that the isotope 29Si is very valuable for NMR research, severe technical difficulties had to be overcome before silicon spectra could be recorded. This was due to the low sensitivity of the isotope resulting from its low gyro magnetic ratio, its low abundance and the rather long relaxation times. The introduction of the Fourier-Transform-Technique (FT-NMR) helped to surmount most of these problems, with the result, that more and more papers concerning silicon NMR appear. Thus, it seems now that most of the salient features of 29Si-NMR are known today. Some resume of the state of the art of 29Si_NMR have been reported [1-4]. Although the theory of 29Si-NMR is not yet understood beyond the basic features, it promises to be of value mainly for two reasons: 1. Silicon is strategically located in the Periodic Table of the elements between the elements carbon, aluminum and phosphorus. For an unified theory of chemical shifts and coupling constants of the heavier elements silicon NMR values will be important. 2. The normal coordination number of silicon is four. If the current view of the chemical shifts of the heavier elements is correct, then the paramagnetic part is dominant for the measured shift data. Two of the parameters used for the calcu lation of the paramagnetic part are bond orders and angles. Bond angles are rare ly determined experimentally with high precision.

With the power and range of modern pulse spectrometers the compass of NMR spec troscopy is now very large for a single book-but we have undertaken this. Our book covers the Periodic Table as multinuclear spectrometers do, and introductory chapters are devoted to the essentials of the NMR experiment and its products. Primary products are chemical shifts (including anisotropies), spin-spin coupling constants, and relaxation times; the ultimate product is a knowledge of content and constitution, dynamic as well as static. Our province is chemical and biochemical rather than physical or technical; only passing reference is made to metallic solids or unstable species, or to practical NMR spectroscopy. Our aim is depth as well as breadth, to explain the fundamental processes, whether of nuclear magnetic shielding, spin-spin coupling, relaxation, or the multiple pulse sequences that have allowed the development of high-resolution studies of solids, multidimensional NMR spectroscopy, techniques for sensitivity enhancement, and so on. This book therefore combines the functions of advanced textbook and reference book. For reasonably comprehensive coverage in a single volume we have sum marized the information in tables and charts, and included all leading references.