Spectroscopic Properties of Inorganic and Organometallic Compounds : Volume 14

ISBN 10: 0851861237 / ISBN 13: 9780851861234

Verlag: Royal Society of Chemistry, The, 1981

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Former library copy. Pages intact with possible writing/highlighting. Binding strong with minor wear. Dust jackets/supplements may not be included. Includes library markings. Stock photo provided. Product includes identifying sticker. Better World Books: Buy Books. Do Good.

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Bibliografische Details

• Titel: Spectroscopic Properties of Inorganic and Organometallic Compounds : Volume 14
• Verlag: Royal Society of Chemistry, The
• Erscheinungsjahr: 1981
• Sprache: Englisch
• ISBN-10: 0851861237
• ISBN-13: 9780851861234
• Einband: Hardcover
• Auflage: Review of 1980 Literature.
• Zustand: Very Good
• Gewicht: 1,53 Pfund

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Inhaltsangabe

Spectroscopic Properties of Inorganic and Organometallic Compounds provides a unique source of information on an important area of chemistry. Divided into sections mainly according to the particular spectroscopic technique used, coverage in each volume includes: NMR (with reference to stereochemistry, dynamic systems, paramagnetic complexes, solid state NMR and Groups 13-18); nuclear quadrupole resonance spectroscopy; vibrational spectroscopy of main group and transition element compounds and coordinated ligands; and electron diffraction. Reflecting the growing volume of published work in this field, researchers will find this Specialist Periodical Report an invaluable source of information on current methods and applications. Specialist Periodical Reports provide systematic and detailed review coverage in major areas of chemical research. Compiled by teams of leading experts in their specialist fields, this series is designed to help the chemistry community keep current with the latest developments in their field. Each volume in the series is published either annually or biennially and is a superb reference point for researchers. www.rsc.org/spr

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Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 14

A Review of the Recent Literature Published up to late 1980

By D. M. Adams, E. A. V. Ebsworth

The Royal Society of Chemistry

Copyright © 1981 The Royal Society of Chemistry
All rights reserved.

ISBN: 978-0-85186-123-4

Contents

Chapter 1 Nuclear Magnetic Resonance Spectroscopy By B. E. Mann, 
Chapter 2 Nuclear Quadrupole Resonance Spectroscopy By K. B. Dillon, 
Chapter 3 Rotational Spectroscopy By S. Cradock, 
Chapter 4 Vibrational Spectra of Small Symmetric Species; Single-crystal and Other Solid-state Spectroscopy By D. M. Adams and P. D. Hatton, 
Chapter 5 Characteristic Vibrations of Main-group Element Compounds By S. Cradock, 
Chapter 6 Vibrational Spectra of Transition-element Compounds By J. S. Ogden, 
Chapter 7 Vibrational Spectra of Some Co-ordinated Ligands By G. Davidson, 
Chapter 8 Mössbauer Spectroscopy By J. D. Donaldson, S. M. Grimes, and M. J, Tricker, 
Chapter 9 Gas-phase Molecular Structures Determined by Electron Diffraction By G. Gundersen and D. W. H. Rankin, 

CHAPTER 1

Nuclear Magnetic Resonance Spectroscopy

BY B. E. MANN

1 Introduction

Following the criteria established in earlier volumes, only books and reviews directly relevant to this chapter are included, and the reader who requires a complete list is referred to the Specialist Periodical Report 'Nuclear Magnetic Resonance', where a complete list of books and reviews is given. Reviews which are of direct relevance to a section of this report are included in the beginning of that section rather than here. Papers where only 1H n.m.r. spectroscopy is used are only included when the 1H n.m.r. spectra make a non-routine contribution, but complete coverage of relevant papers is still attempted where nuclei other than the proton are involved.

Only one relevant book has appeared during 1980, namely 'E.P.R. and N.M.R. in the Chemistry of Coordination Compounds'. Numerous reviews have appeared, including 'Correlations in Nuclear Magnetic Shielding, Part II', 'N.M.R. Spectroscopy of Organometallic Compounds of the f-Elements; Practical Applications', 'N.M.R. for Rare Earth Complexes; Theory', 'N.M.R. of Other Nuclei', 'Application of N.M.R. in the Structure Elucidation of Coordination Compounds: Metal Nuclei', 'Nuclear Magnetic Resonance of the Less Common Quadrupolar Nuclei', 'Carbon-13 and Nitrogen-15 N.M.R. Studies in Organic and Organometallic Chemistry', σ,π-Conjugation in Organometallic Systems', 'Dynamic and Stereochemical Studies by Phosphorus-31 N.M.R. Spectroscopy on Polyphosphine Complexes of Heavy Metals', 'Phosphorus-31 N.M.R. Studies of Catalytic Systems Containing Rhodium Complexes of Chelating Diphosphines', 'Model Compounds as Aids in Interpreting N.M.R. Spectra of Haemoproteins', 'High Resolution N.M.R.', a review of n.m.r. properties of metal nuclei in metallo-proteins, 'Nuclear Magnetic Resonance Spectroscopy of Diamagnetic Porphyrins', 'Biophysical Applications of N.M.R. to Phosphoryl Transfer Enzymes and Metal Nuclei of Metalloproteins', 'Multinuclear N.M.R. Studies of Crown and Cryptand Complexes', 'Synthesis, Molecular Dynamics, and Reactivity of Mixed-Metal Clusters', and 'Nuclear Magnetic Resonance in Molten Salts and Molten Metal–Salt Mixtures. I. Chemical Shift'.

A number of papers have been published which are too broadly based to fit into a later section and are included here. J(15N, 13C) and 15N/14N isotope effects on 13C chemical shielding have been reported for [Cu(CN)4,]3-, [Ni(CN),]2-, [Pt(CN),]2-, [Cd(CN)4]2-, and [Hg(CN)4]2-. The isotope shifts, 0.02 — 0.04 p.p.m, are comparable to recently reported 16O/18O isotope effects on 13C chemical shielding in metal carbonyl derivatives. The H chemical shifts of 2-hydroxy-1,3-propanediamine-NNN'N'-tetra-acetic acid and 1,3-propanediamine- NNN'N'-tetra-acetic acid in 1:1 complexes with diamagnetic metal ions have been investigated as a function of the metal ion charge z and crystal ionic radius r. The chemical shifts correlate with z/r linearly. 1H and 31P n.m.r. spectra have been recorded for complexes of ATP with MgII, CaII, SrII, ZnII, CdII, SnII, PbII, HgII, AgI, and TlI. Each of these ions, except HgII, affected the 13P n.m.r. of ATP, usually shifting all three resonances to high frequency and decreasing J(31P,31P). PbII exerted the greatest shifts, whereas MgII caused the greatest change in coupling constant. In 13C n.m.r. spectroscopy the intensities of different signals become almost equal on adding Cr(acac)3 as a relaxation reagent.

15N n.m.r. spectra of nitrogen-containing crown ethers, cryptand ligands, and other ligands with pyridine-type nitrogens and their complexes with alkali, alkaline-earth, AgI, and TlI ions have been reported. An analytical LCAO MO theory of the Fermi contact term, 1K (A, 19F), has been developed for substituted planar-trigonal AF3 - n Ln and tetrahedral AF4 - n Ln fluorides of main-group elements. This treatment was extended to octahedral cases. For melts of transition, alkali, and alkaline-earth metal fluorides a theory about the effect of outer-sphere cations on the chemical shift of the 19F nucleus entering into the [MF4]n - 4 complex ion has been developed. The changes in the chemical shift of a central-atom nucleus during successive substitution of ligands in the AXk-nYn-type molecular systems have been explained.

2 Stereochemistry

This section is subdivided into ten parts which contain n.m.r. information about lithium, magnesium, and transition-metal complexes, presented by Groups according to the Periodic Table. Within each Group, classification by ligand type.

Complexes of Group IA and IIA. — The 3J (13C, 1H) and 1J(13C 13C) in EtM, Pr1M, and ButM (M = alkali metal or halogen) have been determined. The substituent electronegativity dependence of 3J(13C,1H) shows that the influence exerted by a β-Me substituent on 3J(13C,1H) and 2J (13C,1H) is not constant. The σ- vs. π-character of R2CR1=CR3CH 2M (M = Li, K, or MgBr) has been studied via13C n.m.r. spectroscopy.

INDO molecular-orbital calculations have suggested that 1J (13C, 7Li) in methyl-lithium monomer should be 16 Hz. The 13C n.m.r. shifts in straight-chain alkyl-lithium compounds in ether and cyclopentane are linear with those of the corresponding hydrocarbons, indicating that the whole series of compounds studied have similar electronic structures about the bridged carbon-lithium bonds. The C1, 13C n.m.r. resonance in PrLi broadens with decreasing temperature, indicating the operation of interaggregate bond exchange as well as lithium quadrupole relaxation. 13C n.m.r. spectra of allyl-lithium-1-d have been reported which are consistent with a symmetric rather than a rapidly equilibrating unsymmetric structure. 1H and 13C n.m.r. spectra of a series of para-substituted α-methyl-α-neopentylbenzyl-lithium indicate a Hückel charge distribution. For some 9-alkyl-10-lithio-9, 10-dihydroanthracenes the para n.m.r. shift has been investigated as a function of solvent.

The magnetic moment of 24mNa is 1.930(3) nuclear magnetons (uncorrected). The Na n.m.r. spectrum of Na{CH(PPh2CHPh)2} (thf) shows an asymmetric ligand arrangement with a 2200 Hz linewidth. 1H, 13C, and 31P n.m.r. spectra were also recorded. The 13C n.m.r. spectrum of C5H7 K has also been reported. The 31P skeleton of...