Spectroscopic Properties of Inorganic and Organometallic Com
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Reflecting the growing volume of published work in this field, researchers will find this book an invaluable source of information on current methods and applications.InhaltsverzeichnisNMR Spectroscopy in the Liquid and Gas Phase So.
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- Title
- Spectroscopic Properties of Inorganic and Organometallic Com
- Author
- Mann, Brian E.
- Publisher
- Royal Society of Chemistry
- Publication year
- 2003
- Condition
- New
- Binding
- Hardcover
- Language
- English
- ISBN 10
- 0854044418
- ISBN 13
- 9780854044412
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 36
A Review of the Literature Published up to late 2002
By G. DavidsonThe Royal Society of Chemistry
All rights reserved.
Contents
Chapter 1 NMR Spectroscopy in the Liquid and Gas Phase By B.E. Mann, 1,
Chapter 2 Solid State NMR Spectroscopy By B.E. Mann, 122,
Chapter 3 Nuclear Quadrupole Resonance Spectroscopy By K.B. Dillon, 19,
Chapter 4 Characteristic Vibrations of Compounds of Main Group Elements By G. Davidson, 212,
Chapter 5 Vibrational Spectra of Transition Element Compounds By G. Davidson, 261,
Chapter 6 Vibrational Spectra of Some Co-ordinated Ligands By G. Davidson, 307,
CHAPTER 1
NMR Spectroscopy in the Liquid and Gas Phase
BY B.E. MANN
1 Introduction
In order to reduce the length of individual chapters, this report on 'NMR Spectroscopy' has been divided into two chapters: 'Solution and Gas Phase NMR Spectroscopy' and 'Solid-State NMR Spectroscopy'.
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 Reports '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, 2H, 13C, 19F, and/or 31P NMR spectroscopy is used are only included when they make a non-routine contribution, but complete coverage of relevant papers is still attempted where nuclei other than these are involved.
Several reviews have been published which are relevant to this review: 'Connectivities in molecules by INADEQUATE: recent developments', which contains 29Si and 183W NMR spectra, 'Temperature measurements using nuclear magnetic resonance', which describes various thermometers based on 1H, 13C, 15N, 119Sn and 207Pb, 'Multiquantum filters and order in tissue', which contains 23Na NMR spectroscopy, 'Applications of advanced experimental techniques: high pressure NMR and computer simulations', '2H NMR relaxation as a method for characterisation and study of transition metal hydride systems in solution', 'NMR relaxation studies of polynuclear hydrides derivatives', 'A Half-century of nonclassical organometallic chemistry: A personal perspective', 'NMR studies of metal complexes and clusters with carbonyls and phosphines', 'Adventures in organometallic NMR: steric restraints, slowed rotations, and skeletal rearrangements', 'Applications of pulsed-gradient spin-echo (PGSE) diffusion measurements in organometallic chemistry'," 'Metal ion-assisted interactions involving biological molecules. From small complexes to metalloproteins', '113Cd and 207Pb NMR spectroscopic studies of calcium-binding proteins', 'Local and band susceptibility on π-d hybridised organic-inorganic system disclosed by site-selective NMR', and 'Relaxation and dynamics of molecules in the liquid crystalline phases'.
A number of papers have been published which are too broadly based to fit into a later section and are included here. NMR chemical shifts have been calculated for H2, N2, NH3, CH4, C2H4, HCN, MeCN and H2O. The magnetic shielding has been calculated for [CO3]2-, [NO3]-, [SO4]2- and [N]3-. Calculated and experimental 15N shifts of NaN5, KN5, Mg(N5)2, Ca(N5)2 and Zn(N5)2 have been reported. 31P and 35Cl PGSE diffusion studies have been applied to phosphine ligands and selected organometallic complexes. The direct determination of 119Sn, 195Pt, 199Hg and 204Pb NMR correlation times from spin-lattice and spin-spin relaxation times has been described. 3He, 11B, 21Ne, 27Al and 69Ga NMR chemical shifts have been calculated for icosahedral closo-borane, -alane and -gallane dianions with endohedral noble gas atoms and their lithium salts. The nuclear magnetic shielding polarisabilities of N2, F2, CO, HF, HCl, HCN, HNC and C2H2 have been computed. The 19F NMR chemical shieldings of M1F2, M1 = Zn, Cd, Pb, M2F2, M2 = Al, Ga, In, and SnF4, have been studied by the GIAO-B3LYP method.
2 Stereochemistry
This section is subdivided into eleven parts which contain NMR information about Groups 1 and 2 and transition-metal complexes presented by Groups according to the Periodic Table. Within each Group, classification is by ligand type.
2.1 Complexes of Groups 1 and 2. – 87Rb-129Xe spin exchange and relaxation rates have been measured at high pressure and high magnetic field. 1J(1H-1H) and 3J(M-X) coupling constants have been examined as fingerprints for hydrogen bond type. The 7Li NMR spectra of [Li2C4Ph2(SiMe3)2] indicate that the two lithium atoms are considerably shielded by the ring current. NMR data have also been reported for [LiBun], (6Li), [LiCH2-2-(1-Me-imidazole)], (6Li), [Li(THF)4][Li{C(SiR3)Ph2}2], (7Li, 29Si), [CuLi2CN)], (6Li), [({(S)-α-(PhCHMe)(CH2CH = CHLi)N})Li]6, (7Li), [LiButLiC6H3-2,6(C6H2-2,4,6- Pri3)2], (7Li), [MLi2XAr2], (M = Cu, Ag, Au; 6Li), (1), (7Li), [Li{Si({NCH2But} 2C6H4-1,2)R}L], (7Li, 29Si), [(But2MeSi)3MLi], (M = Si, Ge; 29Si), [Na{C(SiMe3)Ph2}]n (23Na, 29Si), and [Cs(PC4Me4)], (133Cs).
6LiH HOESY experiments have shown that in (2), lithium prefers the five-membered chelate while sodium prefers the six-membered chelate. 15N T1 measurements have been used to study Li+ binding to the nitrogens in polyphosphazenes. 7Li1H HOESY has been applied to probe solvent-cellulose interactions in cellulose dissolution. The relaxation characteristics in the 17O NMR spectra of Na+ and K+ water clusters have been reported. 23Na and 31P NMR spectra have been used to study the time course of myocardial sodium accumulation after burn trauma. The phase behaviour of a mixture of phospholipid bicelles has been investigated using 2H, 23Na and 31P NMR spectroscopy. 1H and 13C NMR chemical shifts have been calculated for Ag+, K+ and Rb+ salts of hydroorotate (2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylate) anion. 87Rb MRI has been used to follow Rb+ uptake in pig hearts. NMR data have also been reported for [Li4B(N-2-pyridyl)3(NH-2-pyridyl)(THF)3], (7Li, 11B), [LiMg(NPri2)2(OR)]2, (7Li), [ArfC(NSiMe3)2Li]n, (29Si) [PhCH2NLiN-(SiMe3)CH2Ph], (7Li, 29Si), [Li{μ-N(SiMe3)2}2 Ca{N(SiMe3}2], (7Li), [Li{Si[(NCH2But)2C6H4-1,2]R}(THF)2], (7Li, 29Si), [(C6H4-1-OMe-2- NSiMe3)Li(OEt2)]2, (7Li), [(But2SiFLiNBut)2OEt2)], (29Si), [1,8-{(Me3SiN)Li(THF)}2C10H6], (7Li, 29Si), [{Me2Si(2,6- Pri2C6H3)NLi}2]2, (7Li, 29Si), [2-PhC6H4NLi2]n [2-PhC6H4N{B(NMe2)2}2], [2- PhC6H4N(SiMe3)2], (7Li, 11B, 29Si), [Li{N(C6H3Me2- 2,6)CC(SiMe3)Si(SiMe3)2N(C6H3Me2-2,6)}(tmeda)], (7Li), [Li2{C6H4-1,3-(CH2NC6H3-2,6- Pri2)2}], (7Li), [Yb{(N{SiMe3}CPh)2CH-μ-Li(THF)}2], (7Li, 29Si), [Li{Me2(MeO)SiNC(Ad)-CHSiMe3}2], (7Li, 29Si), [Li2(THF){P(O)(NBut)2(NHBut)}]2, (7Li),62 (3), (7Li, 29Si), [CyPSe3Li2(tmeda)2], (77Se), [(THF)2Li2{PhP(Se)(NBut)2}2], (7Li, 77Se), [Li(tmeda)2][Te(NBut)P(μ- NBut)2P(NBut)Te], (7Li, 125Te), [{As(NBut)3}2Li6], (7Li), [{Sb(μ-NCy)2(μ- N)}3{Li(THF)}3], (7Li, 14N), [M{N(SiMe3) = CC6H3-2,6-Me2}2SiSiMe3], (29Si), Li+ in polyacrylonitrile-based electrolytes, (7Li), Li containing lipophilic nucleosides, (7Li), [{(2-O-4-Me- quinoline)Li}8 (THF)4], (7Li), Li-crown ether complexes, (7Li), [M3L3], {M = Li, Na; L = (4); 7Li, 23Na}, [Li6K6M(Pri3SiP)6(OSiMe3)2], (M = Sr, Ba; 7Li, 29Si), [(But3SiO)4Na4],(29Si),76 and Cs+ in phosphonato cavitands, (133Cs).
2.2 Complexes of Group 2. – Two relevant reviews have appeared: '23Ca NMR of calcium-binding proteins' and 'Shape and dynamics of calcium-binding protein investigation by 15N NMR relaxation'.
The quadrupole moments of 41Ca and 41Sc have been determined. Evidence of a near-critical solvation effect on rotational correlation time of 9Be NMR T1 of [Be(acac)2] has been obtained in liquid and supercritical CO2. The 1H and 13C NMR signals of bacteriochlorophyll a have been assigned. NMR chemical shifts of [ML2], M = Mg, Ca, Sr, Ba, L = [2,6-Pri2C6H3NCMeCHCMeNC6H3-2,6- Pri2] point to increased ionicity of the ligand-metal bond in the order Mg
2.3 Complexes of Group 3, the Lanthanides, and Actinides. – The quadrupole moment of 41Sc, and the magnetic moment of 48Sc, have been determined. Three isomers of [Tm/C82] have been studied by 13C NMR spectroscopy. 1J (89Y31P) = 144 Hz and 1J (31P1H) = 201 Hz in [(THF){1,3-(Me3 Si)2C5H}2Y{PH(SiButS)}] U NMR chemical shifts have been calculated for some diamagnetic uranium compounds. NMR data have also been reported for [{HB(3,5-But, Me-C3HN2)3}Yb(μ-D)]2, (2H, 171Yb), [Li(THF)4] [Yb{CH (SiMe3)2}3], (7Li, 29Si, 171Yb), [Y(η5:η 1-C5Me4CH2SiMe2 NBut)(μ-2-C4H3O)]2, (89Y), [(η5-C5H5) 2Y{N(SiMe3)2PPh2}2 CH2], (29Si), [(η6-3,5-Me2 C5H3BNMe2)2Y(μ-Cl) 2Li]2, (7Li, 11B), [({(Et2CH2CH2NCMe)2CH} Mg-Br)2ScBr], (45Sc), [Sc(acac)2 (μ-Cy7Si8O12)]2, (29Si), [ScXx(OPMe3)6-x], 3-x (45Sc), [Y{μ-OPri)2 M(OPri)}3], (M = Nb, Ta; 89Y), and [Yb(NPh)2(THF)4], (171Yb).
2.4 Complexes of Group 4. – The 1H and 13C chemical shifts of [(η5-C5H5) Zr(μ-Me)AlMe3][Me2AlO] and [(η 5-C5H5)2ZrMe][Me2 AlO] have been calculated and compared with experiment. The size of the ion pair, [(η5-C5H5)2 Zr(μ-Me)AlMe3][Me2AlO], has been determined by PFG NMR spectroscopy. 1H-1H TOCSY and 1 H-1H NOESY have been used to study the structures of a series of substituted indenyl titanium and zirconium complexes. The reactivity of some substituted cyclopentadienyl zirconium chloride/[Me AlO]n towards H2 has been correlated with 91Zr chemical shifts.10H-H NOESY has been used to identify [{η 5-1-(2-MeOC6H4)-indenyl}2 ZrCl2]. There is a correlation of 13C NMR and IR data for a zirconacyclopropene. The coordinative interaction of various organoaluminiums with [ZrCl4] has been studied using 1H and 27Al NMR spectroscopy. NMR data have also been reported for [(η5-C5H5) Zr(μ-H)2BC5H10], (11B), [Ti(CH2SiMe3)(NMe2){MeN (CH2-2-pyrrole)}], (14N), [MeSi{SiMe2 N(C6H4-4-Me)}3SnZr(η5-C 5H5)2Me], (29Si, 119Sn), [Zr3Al(μ4-O)(μ-OMe)6Cl6 Me(THF)3], (27Al), [(η5-C5 Me5)Hf(η4-C6H10)(CH2 SiMe3)], (29Si), (5), (29Si), [{(Me3Si)2N}(C2H4Si2 Me4N)-Ti(C[equivalent to]CR)2], (11B, 15N, 29Si), [(2,6-Pri2C6 H3)N = Hf(THF)2(SiPh3)2], (29Si), [η5-C5H3C5 H8)2Ti(η2-Me3SiC[equivalent to] CSiMe3)], (29Si), (6), (15N), [(η5-C5H5){η5-(Et 3SiCH2CH2)3SiC5 H4}TiCl2], (29Si), (7), (15N), (8), (29Si), [(η5-C5 H5)-(OC)2FeCH2SiMe2OZrCl (η5-C5H5)2], (29Si), [(η5-C5H5)2Zr(μ-O2 BC6H2-2,4,6-Me3)], (11B), [(η5-C5Me5)(η6-C5 H5BCH = CHPh)ZrCl2], (11B), (9), (11B), [Tl4,Ti2(μ-O)(μ3-OEt) 8(OEt)2], (205Tl), [{9-(Me3Si) fluorenyl}4O12(TiOBut)4], (29Si), [(H2C = CH)Cy6Si7O 12TiOPri], (29Si), [(Zr6NCl 12)Cl6]3-, (15N), and [(Me 2NCH2CH2NMe2)HfCl2 {Si(SiMe3)3}], (29Si).
2.5 Complexes of Group 5. – The 31P and 51V NMR spectra of [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] show 51V coupling. NMR data have also been reported for [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] (11B, 29Si), [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] (29Si), (10), (11C), (11), (11B), (12), (7Li), [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] (29Si), [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] (15N), (7Li, 29Si).
The 14N NMR signals of the terminal and bridging imido groups of some imidovanadium complexes show marked differences in their lineshapes that could be used as an additional criterion for signal assignment. NMR data have also been reported for [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] (13), (51V), 1: complexes between aryl hydroxamic acids and vanadate, (15N, 51V), [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] (51V), vanadyl complexes of [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] (51V) [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] (L = tridentate aryloxy ligand, 15N), and (14), (29Si).
(Continues...)
Excerpted from Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 36 by G. Davidson. Copyright © 2003 The Royal Society of Chemistry. Excerpted by permission of The Royal Society of Chemistry.
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6.1 The delivery conditions, delivery date and existing supply restrictions, if applicable, can be found by clicking the appropriate button on our website or in the respective quote.
Unless a different period is specified in the item description or our delivery conditions, the goods are delivered within 3-5 days after the conclusion of the contract (in case an advance payment has been agreed upon, after the payment authorisation).
6.2 If you are a consumer, the following is statutorily regulated: The risk of the sold item accidentally being destroyed or degraded during shipping only passes over to you when the item in question is delivered, regardless of whether or not the shipping operation is insured. This condition does not apply if you have independently commissioned a transport company that has not been specified by us or a person who has otherwise been appointed to execute the shipping operation.
If you are a businessman, the delivery and shipping operations take place at your own risk.
- Statutory warranty right
Liability for defects is governed by the “Warranty” provisions in our General Terms and Conditions of Business (Part I).
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