31P and 13C NMR of Transition Metal Phosphine Complexes

Paul S. Pregosin, Roland W. Kunz (Autoren)

Buch | Softcover

IX, 158 Seiten

2012
Springer Berlin (Verlag)
9783642488320 (ISBN)

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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.

A Motivation and Methodology.- I Introduction.- II Measurement Techniques.- III Spin-Lattice Relaxation Times.- IV The 31P Nuclear Overhauser Effect.- B Coupling Constants.- I One-Bond Metal-Phosphorus Coupling Constants.- II Two-Bond Phosphorus-Phosphorus Coupling Constants.- III One-Bond Metal-Phosphorus Coupling Constants - A Survey.- IV Two-Bond Phosphorus-Phosphorus Coupling Constants - Data.- C Chemical Shifts.- D Applications.- E 13C Studies of Phosphorus Containing Complexes.- I Studies of Coordinated Phosphorus Ligands.- II Studies of Non-Phosphorus Ligands in Phosphorus-Complexes.- F Appendices.- A The Influence of Tr-Orbitals on the Coupling Constant.- B Numerical Values of |?ns(O)|2.- C Differences in 1J(M,P), 2J(P,P)cis and 2J(P,P)trans.- G Tables.- H References.

Erscheint lt. Verlag	14.4.2012
Reihe/Serie	NMR Basic Principles and Progress
Zusatzinfo	IX, 158 p.
Verlagsort	Berlin
Sprache	englisch
Maße	170 x 244 mm
Gewicht	308 g
Themenwelt	Naturwissenschaften ► Chemie ► Anorganische Chemie
Schlagworte	carbon • Chemistry • Magnetische Kernresonanz • metals • Molecule • Organische Phosphorverbindung • phosphorus • transition element • Transition metal • Übergangselementverbindung
ISBN-13	9783642488320 / 9783642488320
Zustand	Neuware