Spectroscopic Properties of Inorganic and Organometallic Com
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Published by Royal Society of Chemistry, 1980
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- Title
- Spectroscopic Properties of Inorganic and Organometallic Com
- Author
- Adams, D. M.
- Publisher
- Royal Society of Chemistry
- Publication year
- 1980
- Condition
- New
- Binding
- Gebunden
- Language
- English
- ISBN 10
- 085186113X
- ISBN 13
- 9780851861135
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 13
A Review of the Recent Literature Published up to late 1979
By D. M. Adams, E. A. V. EbsworthThe Royal Society of Chemistry
All rights reserved.
Contents
Chapter 1 Nuclear Magnetic Resonance Spectroscopy By B. E. Mann,
Chapter 2 Nuclear Quadrupole Resonance Spectroscopy By K. B. Dillon,
Chapter 3 Microwave Spectroscopy By A.P. Cox,
Chapter 4 Vibrational Spectra of Small Symmetric Species; Single-crystal and Other Solid-state Spectroscopy By D. M. Adams,
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 and M. J. Tricker,
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 that 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.
Several relevant books have been published during 1979. The book 'Phosphorus-31 and Carbon-13 N.M.R of Transition Metal Phosphine Complexes' provides a welcome selective source of data. In addition, 'Nitrogen-15 Nuclear Magnetic Resonance Spectroscopy' and 'N.M.R. in Inorganic Fluorides: Structure and Chemical Bonding' have also appeared. 'N.M.R. Spectra; Its Application to the Organometallic Compounds' has also been reviewed.
A number of papers have been published that are too broadly based to fit into a later section and are included here. N.m.r. spectroscopy has been applied to condensed systems with asymmetric centres. The relaxation, including effects of chemical exchange, of spin-5/2 and -7/2 nuclei has been examined. An analytical perturbation extension of the Pople-Santry theory of the Fermi contact term in reduced spin-coupling constants, 1K(M-L), has been developed for the substituted compounds MLnL'm, where the ligands L have a valence ns orbital. It was found that changes in 1K(M–L) under substitution should typically follow changes in s-contribution to the E–L bond overlap population. Subsequently this treatment was applied to phosphorus(III) compounds and good agreement with experiment was found.
1H relaxation times have been measured for H2 in liquid neon, argon, and krypton. The results of coupled Hartree–Fock computations for the n.m.r. shielding constant have been reported for LiH, HF, and PH3. 13C n.m.r. spectra have been reported for diamagnetic cyano complexes in D2O. Except for (Fe(CN)6]4- the 13C resonance in all the cyano complexes examined is at lower frequency than uncomplexed |CN|- and the range of chemical shift spans 92.5 p.p.m. Chemical shift differences were discussed in terms of changes in σ and π-bonding of |CN|- to the metal ion. 1JMC was observed for [59Co(CN)6]3- (126 Hz), [103Rh(CN)6]3- (33.6 Hz), [195Pt(CN)6]2- (808 Hz), and [195Pt(CN)4]2- (1034 Hz). T1, values were also reported for selected compounds and interpreted as being consistent with scalar coupling to 14N.
The equivalent dipole model of the benzene ring current has been applied to both inter- and intra molecular geometries to give detailed conformational information in n.m.r. studies of metalloporphyrins. 13C chemical shifts have been measured for [SCN]-, [NCO]-, and [SeCN]- in a variety of transition-metal complexes. The effects of cation and solvent changes upon the chemical shifts of the ionic pseudo-halides were determined. Changes in hybridization are more important than electron excitation energy changes and substitution changes in determining chemical shifts for both ionic and complexed species. The ordering of the ions in terms of increasing shielding is [SCN]-< [OCN]-< [SeCN|-. The ordering of [SCN]- and [SeCN]- in terms of increasing shielding as a function of bonding mode is M-NCS < [NCS]-< M-SCN. Unsupervised 13C n.m.r. pattern recognition has permitted the qualitative classification of NN-dialkyldithio-carbamate complexes into five classes: free ligands, complexes of main-group elements, and complexes of transition metals, with the latter two groups being divided by a free oxidation number of 0.5 or greater than 0.5. Within the transition-metal complexes metals with electron configuration d6 or d8 and d0 or d]10 can be further distinguished. The class of main-group elements is subdivided into organic dithiocarbamates and a subclass of main-group element complexes. Changes of 31P chemical shifts during co-ordination of phosphoryl compounds have been discussed.
The 17O n.m.r. shifts of some metal carbonyls are 400 to 300 p.p.m. to high frequency from 17OH2. The δ(17O) trends are generally opposite to those for the carbon monoxide 13C chemical shifts and this is explained by metal π-back-bonding in carbon monoxide π*-orbitals. A metal-triad effect is observed for 17O chemical shifts. There is a low-frequency shift of δ(17O) on descending a given group in the Periodic Table. Over 100 17O n.m.r. chemical shifts have been reported for 27 diamagnetic polyoxoanions of the early transition metals. Efficient procedures for obtaining 17O-enriched compounds were described and the factors controlling sensitivity and spectral resolution are examined and discussed in detail. Comparison of chemical-shift values with structural data shows that chemical shifts are determined largely by metal-oxygen bond strengths. As complexes of 3-mesitylacetylacetone show very small chemical-shift differences between their o- and p-methyl signals, 0.11 to 0.23 p.p.m., it was concluded that they do not possess magnetic anisotropies in the chelate rings comparable with those of benzene. The nature of the ligand L and the position of the resonance lines of non-equivalent fluorine atoms in the 19F n.m.r. spectra of pseudo-octahedral fluoro complexes have been reviewed.
2 Stereochemistry
This section is subdivided into ten parts containing n.m.r. information about lithium, magnesium, and transition-metal complexes, presented by Groups, according to the Periodic Table. Within each Group classification is by ligand type.
Complexes of Groups IA and IIA. — 1H n.m.r. spectroscopy has been used to determine the concentration of n-butyl-lithium. In the anionic polymerization of 1-phenyl-1,3-butadiene the propagating species was shown by 1H and 13C n.m.r. spectra to be the 4,1-anion. The 13C n.m.r. spectra of (1) and related compounds have been reported, while for LiCBr31J(13C, 7Li) is 43 Hz. Low-temperature 13C n.m.r. spectra of some lithiated chiral oxazolines show the presence of two isomers. 1H n.m.r. spectra have been used to show chair conformations for complexes of sparteine and α-isosparteine with Li+.
From 1H n.m.r. spectroscopy it has been concluded that tetracyanoquinodi-methane interacts with chlorophyll by a donor–acceptor mechanism with the nitrogen atom of the second ring of the pigment molecule acting as p-donor.
1H and 13C n.m.r. spectra of the alkaline-earth and diamagnetic rare-earth metal complexes of diethylenetriaminepenta-acetate have been discussed in terms of the labilities of the metal–oxygen and metal–nitrogen bonds. The various resonance-splitting patterns observed in the alkaline-earth spectra were correlated with the patterns predicted for possible hexadentate structures involving all three nitrogen donors and averaging for the other three co-ordination sites by four of the ligand carboxylate groups. A heptadentate structure was proposed for the complexes with the lanthanides.
Complexes of Y, La, Lu, U, Ti, Zr, Zr, Hf, and Th. — An examination of the 89Y n.m.r. chemical shifts for several inorganic salts in aqueous solution in the pH range 0 — 6 showed little or no change, indicating that Y T2 values are not pH-dependent. The resonances are always very sharp (half-widths ca. 0.3 Hz) and probably limited only by magnet homogeneity. Certainly there is no reduction in signal-to-noise ratio in this pH range. The observation of 2J(89Y, 31P) in [Y{S2P(OEt)2|4]- has been interpreted as evidence for covalent bonding. The magnitude of 2KYP is of the same order as 2KRhP and 2KPtP in [Rh(S2P(OEt2)2}3] and [Pt{S2P(OEt)2}2], indicating similarity in the covalent contribution to their bonds.
The g-factor of the first excited state in 138La has been measured by the time-differential perturbed angular distribution method. A 180 MHz 1H n.m.r. study of the lanthanide (2.2.1)cryptates in CD3CN and D2O solution has been performed. The compound [La(2.2.1)]3+ is the first example of an f-orbital co-ordination complex to exhibit a strong ligand conformation preference. Moreover, a 1H n.m.r. examination of the various paramagnetic [Ln(2.2.1)]3+ ions has demonstrated that these species are quite similar in structure across the entire series. N.m.r. data have also been reported for [{YCp2Me}2] (13C), [M(NNN'N-tetramethyl-α-carboxamidoanisamide)3] (M = Y. La; 13C), [Lu(CH2SiMe3)4]- (13C), [{(Me3Si)2N}2M(µ-CH2)(µ-NsiMe3)SiMe2 (M = Th, U; 13C), [UO2(OC{CF3)3}2 (THF)2] (19F), and [U(OMe)F5] (13C, 19F).
For [Th{(CH2)nC5H4}2X2] the varying degrees of splitting between the high-field portions of an A2B2 resonance pattern due to the cyclopentadienyl hydrogen atoms have been interpreted in terms of bonding geometries. The 13C n.m.r. spectra were also reported. According to 19F n.m.r. spectra TiF4 reacts with phosphoryl-containing ligands to give cis-[TiF4L2. With decreasing donor capacity of L the 19F n.m.r. signals are shifted to high frequency. Significant shifts were observed for the 19F atom trans to Bu3PO and Bu3PO4. 13C shielding parameters have been determined for the N-phosphorylated aniline and O-phosphorylated phenol derivatives PhYP(O)Z2 (Y = NH, O) and for their complexes with TiCl4. Inductive and resonance substituent parameters were calculated. N.m.r. data have also been reported for [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII].
On the basis of 31P n.m.r. spectroscopy [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] dissociates in solution to [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII]. 13C n.m.r. spectroscopy has been used as a probe of electron density on nitrogen in Group IVA and Group VA t-butylimido derivatives. 13C n.m.r. spectroscopy has been used to show that commercial [HfCp2Cl2] contains ca. 10% zirconium. N.m.r. data have also been reported for [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII].
Complexes of V, Nb, and Ta. — The 51V n.m.r. spectrum of [(Me3SO)3V=NBut] shows a 14N coupling of 95 Hz. The compositions and structures of vanadium oxyfluorochloro complexes formed by the reaction of VOCl3 with HF or KF in MeCN solutions have been studied by 51V n.m.r. spectra. Some phosphoro-vanadium complexes have been studied in solution by n.m.r. Peroxovanadium(v) species of notional formulae [VO(O2)]+, [HVO2(O2)2]2-, [H2VO2(O2)2]-, [VO(O2)3]3-, [HVO(O2)3]2-. [V(O2)4]3-. [H{VO(O2)2}2O]3-, and [VO(NH3)-(O2)]- have been identified in aqueous solution by 51V n.m.r. spectroscopy and the pKa determined. 51V n.m.r. spectra of vanadyl esters dissolved in nematic liquid crystals show a seven-line system, which is due to a first-order quadrupole interaction. Quadrupole splittings vary from 3.6 to 1.93 kHz. N.m.r. data have also been reported for [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII].
A high-resolution n.m.r. study of [{Nb(tetraphenylporphyrin}O2O3} and |Nb(tetraphenylporphyrin)(O)(O2CMe)xnMeCO2H] has been claimed to show that the anisochrony of the methylenic protons is induced by the out-of-plane position of the metal atom. However, it would appear that the true cause is the presence of different ligands on the two sides of the plane. The 93Nb n.m.r. spectra of NbX5, (X = Cl, Br) in MeCN solutions in the presence of HF indicate the formation of [NbFnX6-n] (n = 0-6). NbX5, in MeCN in the presence of KNCS gave [Nb(NCS)nX6-n] and [Nb(NCS)7]2-; similar mixed-ligand anions were observed in the NbX5-KNCO-MeCN systems. 93Nb n.m.r. spectra have shown that the reaction of [NbOCl3] and [NbOBr3] with [NCS]-, [NCO]-, and F- in MeCN yields complexes of the type [NbOXnY4-n(NCMe)]-. 19F n.m.r. chemical-shift data for [NbF3{(RC6H4)3PO)] and [TaF5 {(RC6H4)3PO}] indicate that with increasing basicity of the ligand the 19F n.m.r. signal is shifted to low frequency. T1, and T2, of the 93Nb nucleus were measured as a function of temperature in [NbClnBr6-n]-. The rate of relaxation in all the complexes except fac]NbCl3Br3]- was determined by the quadrupole interaction. In fac-[NbCl3Br3]- the mechanism of relaxation is caused by exchange processes, related to intramolecular cis-trans isomerization. According to the 19F n.m.r. spectra, acetoxime (HL) reacts with TaF5 in MeCN to give [TaLF5]- and cis-[TaF4L2]-. With ethylmethyl ketoxime (HQ) |TaF5(syn-Q)]-, [TaF5(anti-Q), [TaF4(syn-Q)2]-, and [TaF4(anti-Q2)]- are formed. TaL5 reacts with Et3NHF to give trans- and cis-[TaF3L3]-. [TaF5ONCHPh2]- and [TaF4- (ONCHPh)2]- were also formed. The 19F n.m.r. spectra of TaF5 and R3PS show the formation of [TaF5(SPR3)], and the donor capacity of SPR3 was established. The 19F n.m.r. spectrum of equimolar solutions of TaF5 and Ph3AsS in CH2Cl2 indicates the formation of [TaF5(Ph3AsS)], in which the Ph3AsS is co-ordinated through the sulphur atom. Equimolar solutions of TaF5 and R3AsO (R = Ph, Bu) form [TaF5(R3AsO)] and cis- and trans-[TaF4(R3AsO)]+. According to the n.m.r. data, the donor properties of R3AsO are greater than those of Ph3AsS. On the basis of the chemical shift of analogous complexes with [TaF5(OPR3)] and [TaF5(SPR3)], the donor capability for these ligands decreases in the series R3AsO > R3PO > R3AsS ~ R3PS. N.m.r. data have also been reported for [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII].
(Continues...)
Excerpted from Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 13 by D. M. Adams, E. A. V. Ebsworth. Copyright © 1980 The Royal Society of Chemistry. Excerpted by permission of The Royal Society of Chemistry.
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last update: 01.01.2022
Data protection declaration
Unless stated otherwise below, the provision of your personal data is neither legally nor contractually obligatory, nor required for conclusion of a contract. You are not obliged to provide your data. Not providing it will have no consequences. This only applies as long as the processing procedures below do not state otherwise.
“Personal data” is any information relating to an identified or identifiable natural person.
Responsible person
Contact us at any time. The contact details of the person responsible for data processing can be found in our legal notice.
Collection, processing, and transfer of personal data in orders
When you submit an order we only collect and use your personal data insofar as this is necessary for the fulfilment and handling of your order as well as processing of your queries. The provision of data is necessary for conclusion of a contract. Failure to provide it will prevent the conclusion of any contract. The processing will occur on the basis of Article 6(1) b) GDPR and is required for the fulfilment of a contract with you.
Your data is transferred here for example to the shipping companies and dropshipping providers, payment service providers, service providers for handling the order and IT service providers that you have selected. We will comply strictly with legal requirements in every case. The scope of data transmission is restricted to a minimum.
Duration of storage
After contractual processing has been completed, the data is initially stored for the duration of the warranty period, then in accordance with the retention periods prescribed by law, especially tax and commercial law, and then deleted after the period has elapsed, unless you have agreed to further processing and use.
Rights of the affected person
If the legal requirements are fulfilled, you have the following rights according to art. 15 to 20 GDPR: Right to information, correction, deletion, restriction of processing, data portability. You also have a right of objection against processing based on art. 6 (1) GDPR, and to processing for the purposes of direct marketing, according to art. 21 (1) GDPR.
Right to complain to the regulatory authority
You have the right to complain to the regulatory authority according to art. 77 GDPR if you believe that your data is not being processed legally.
Right to object
If the data processing outlined here is based on our legitimate interests in accordance with Article 6(1)f) GDPR, you have the right for reasons arising from your particular situation to object at any time to the processing of your data with future effect.
If the objection is successful, we will no longer process the personal data, unless we can demonstrate compelling legitimate grounds for the processing that outweigh your interests or rights and freedoms, or the processing is intended for the assertion, exercise or defence of legal claims.
last update: 10.01.2022