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.InhaltsverzeichnisNuclear magnetic resonance spectroscopy, B.E. Ma.
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- Spectroscopic Properties of Inorganic and Organometallic Com
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- Carpenter, John H.
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- Royal Society of Chemistry
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- 1993
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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 26
A Review of the Recent Literature Published up to Late 1992
By G. DavidsonThe Royal Society of Chemistry
All rights reserved.
Contents
Chapter 1 Nuclear Magnetic Resonance Spectroscopy By B. E. Mann, 1,
Chapter 3 Rotational Spectroscopy By J.H. Carpenter, 226,
Chapter 4 Characteristic Vibrations of Compounds of Main Group Elements By G. Davidson, 253,
Chapter 5 Vibrational Spectra of Transition Element Compounds G. Davidson, 289,
Chapter 6 Vibrational Spectra of Some Co-ordinated Ligands By G. Davidson, 325,
Chapter 7 Moessbauer Spectroscopy By S.J. Clark, J.D. Donaldson, and S.M. Grimes, 371,
Chapter 8 Gas-phase Molecular Structures Determined by Electron Diffraction D.W.H. Rankin and H.E. Robertson, 463,
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 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, 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. In view of the greater restrictions on space, and the ever growing number of publications, many more papers in marginal areas have been omitted. This is especially the case in the sections on solid-state NMR spectroscopy, silicon and phosphorus.
One book has been published which is relevant to this review:- 'Studies in Inorganic Chemistry, 13: Transition Metal Nuclear Magnetic Resonance', ed. by P.S. Pregosin.
Several relevant reviews have been published, including 'Molecular hydrogen (η2-H2) complexes of transition metals, 'Metal NMR chemical shifts of polynuclear early transition metal complexes with direct metal-metal bonds' 'Electronic states of transition metal complexes and the electronic mechanism of metal-nucleus NMR chemical shifts' 'Synthesis and characterization of heterometallic carbonyl cluster anions', 'Applications of spectroscopic measurements to homogeneous catalysis', and 'Use of NMR spectroscopy in the study of glass structure. I. NMR spectroscopy of silicate solutions'.
A number of papers have been published which are too broadly based to fit into a later section and are included here. The use of 1J(13 C1H) as a criterion of agostic bonding has been examined for C2H4 coordinated to early transition metals. N NMR spectroscopy has been used to probe the bonding, bending and fluxionality of the imido ligand on Ta, Mo, W, Re, and Os. Inorganic phosphates have been analysed quantitatively using 31P NMR spectroscopy.' The solution and solid state conformations of Ni2+, Zn2+, Cd2+, and Hg2+ have been investigated both in solution and the solid state by 13C NMR spectroscopy and in solution by 199Hg NMR spectroscopy. The relaxation and dynamical properties of water in partially filled porous materials have been investigated using NMR techniques. The measurement of I = 5/2 relaxation in biological and macromolecular systems using multiple-quantum NMR techniques has been described and applied to 17O, 25Mg, and 27Al. The characterisation of compounds using 13C and 29Si NMR spectroscopy has been discussed, NMR data have also been reported for 1-Me3Si-cycloocta-1,5-diene complexes with RhI, PdII, PtII, and AgI, (13C), pyridoxalisonicotinoyl hydrazone complexes with some 3 d metal ions, (13C), 17U, Mo, W, Re, Rh, and Pd complexes of (1), (13C), NiII and ZnII complexes of (2), (13C), salicylaldehyde-2-aminobenzophenone-2-thenoylhydrazone complexes with 3d metal ions, (13C), [M(RNCMeCH2CMe2NHR)]2+, (M = Co, Ni, Zn, Cd; 13C), complexes of metals with 1,15-diaza-3,4:12,13-dibenzo-5,8, 11-trioxacyclooctadecane, (13C), and metal complexes of 4-acyl-5-pyrazolone, (13C).
2 Stereochemistry
This section is subdivided into eleven parts which contain n.m.r. 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.
Complexes of Groups 1 and 2. — Reviews entitled 'NMR of lithium-6 enriched organolithium compounds', and 'Applications of NMR in sensory science', which includes Na NMR spectroscopy, have appeared.
The 13C NMR spectrum, including IJ(13 C6Li), has been reported for [LiCH2NMeCH2 CH2-NMeCH2CH2NMe2]. 6Li-6Li COSY of PriLi/sparteine in Et2O shows coupling between two sites. The 13C NMR spectrum was also reported. The structures of [Ph3CLi] and [Cs(3-Et-3-heptoxide)] in solution have been studied using 6Li, 1H HOESY, 133Cs, 1H HOESY, and 1H, 1H ROESY, and close contacts identified. 6Li,1H HOESY has been used to determine Li — H distances to an accuracy of ca 0.2 Å in [C2H3Li.thf]4. The solution structures of [[Li(TMEDA))2(Me3Si-CH=CH)2] and [(Li(TMEDA))2(Me3SiCH=CMe)2] have been determined using 7Li, 1H HOESY. 7Li T1 measurements were also reported. The one-dimensional and two-dimensional 6Li, 6Li INADEQUATE experiments have been described and applied to compounds such as (E)-1-Li-2- (2-LiC6H4)-1-Ph-hex-1-ene. [2-Me2N-6-Bu1 O-C6H3Li] shows extreme distortion of the benzene ring from hexagonal at Li and a very low 1J(13C13C) of 27.8 Hz results. The 6Li NMR spectrum was also recorded. 13C NMR spectroscopy, 6Li,1H HOESY, and HETCOR have been used to determine the structure of (3). 6Li, 13C, and 15N NMR spectroscopic studies have been used to show that [LiNPri2] in neat TMEDA is a dimer. Heteronuclear multiple quantum correlation has been used to correlate 6Li and 15N chemical shifts of mixed aggregates of [6Li, 15N] lithium 2,2,6,6-tetramethylpiperidide with 6LiBr, 6LiCl, and 6Li(OC6H11). The aggregated forms of [LiNPri2] and Li 2,2,6, 6-tetramethylpiperidide in THF have been unambiguously shown to be dimers rather than trimers or higher oligomers by 6Li detection of 15N homonuclear zero quantum coherence. 6Li, 1H HOESY and 13C NMR spectroscopy have been applied to (4). 13C NMR spectroscopy has been used to study the structure of the complex of CH2(CH2O-I-C6H4-2-OCH2) 2CHCH2OP(O)(OH)-(OBun) with Li+. A method has been developed to measure Li+ concentrations in the human brain using in vivo1H and 7Li NMR spectroscopy. NMR data have also been reported for [LiCH(CN)2(H2O)(TMEDA)], (1Li, 1H HOESY, 13C), [(PhC=CLi)4 (TMEDA)2], (13C),' (5),( 13C), (6), [C6H4CH=CHSnBun2], (6Li, 13C, 119Sn), [Li(C6H2Ph3). 2Et2O], (13C),[(Li(2,4,6-But3 C6H2))(LiP(H)(2,4,6-But3C6 H2))]2, (7Li),45 [(Et2N)Ph2 SiLi], (13C), [(2,4,6-Me3C6H2)H2 GeLi], (13C), [((Et2O)Li)2(Ph(Me2N)BB (NMe2)Ph)], (11B), [Li(l2-crown-6)][(THF)Li (µ-NSiMeBut2)2SiBut], (7Li, 13C, 29Si), (7), (6Li, 15N) [Li(PhNPPh2)(OEt2)]2, (7Li), [((BUtNPNC6H2BUt3,2,4, 6) Li)n(Et2O)m], (7Li), (8), (7Li, 13C, 29Si), [(Me3SiN)2-SPhLi]2 OEt2, (6Li, including 6Li, 1H HOESY, 7Li, 13C, 29Si), (9), (7Li, 11B, 13C), and LiHC(O)PH.DME, (13C).
23Na NMR spectroscopy has been used to study the binding of Na+ to N(CH2CH2N=CHXCH=N-CH2CH2)3N, X = 2,5-furyl, 2,6-pyridyl, 2,5-pyrole, or 2,6-4-Me-phenol. The conformation of the potassium salt of lasolocid has been determined by 1H and 13C NMR spectroscopy. K NMR spectroscopy has been used to show the presence of K- and [K(cryptand[2.2.2])]+, when K is dissolved in cryptand. The NMR relaxation behaviour and quadrupole coupling constants of Na and 39K in glycerol have been studied and compared with 39K tissue data. NMR data have also been reported for [NaNPri2], (13C), and [MN(SiMe3) 2], (13C, 29Si, 133C).
1J(9Be1H) has been determined for the first time in [HB(3-BUtC3H2N2)3BeH]. The 9Be and 13C NMR spectra were also recorded. The 9Be chemical shift of [Be(O2C6H4) 2]2- is at δ7.5, indicative of catecholate coordination. The 13C NMR spectrum was recorded. NMR data have also been reported for [Me2Al(µ-NEt2)2MgMe]2, (13C, 27Al), [(C5H5)MgOCH2 CH2NMe2], (13C),[(C5Me5) 2M]. [M(N(SiMe3)2)22] 22, (M = Ca, Sr, Ba; 13C), [(C5Me5)CaN(SiMe3) 2. (THF)3], [(C5Me5)2BaN (SiMe3)2]-, (13C), [(C5 Me5)Ca(OC)2Zr(η5-C5Me5)], (13C) [Ba(fluorenyl)2-(HMPA)2], (13C), [(η5-fluorenyl)2Ba], (13C), [(η3-HB(3-ButC3H2N2) 3)MgO2R], (13C), (17O), [(PhC(NSiMe3)2]2Mg(NCPh)], (13C, 29Si), [(PhNCPh=CPhNPh)2Mg], (13C), (10), (13C), [Me2Ag(CN)(MgBr)2], (13C), [(dibenzopyrryl)2Ca(NC5H5)2], (13C),[(PhC(NSiMe3)2}2M(THF)2], (M = Sr, Ba; 13C, 29Si), [Ca{PhC(NSiMe5) 2)2.2THF], (29Si),(11), (13C), [M(ethyl acetoacetato)2], (M = Mg, Ca; 13C), [M(OC6H2BUt2-2,6-Me-4)2 (THF)2], (M = Ca, Ba; 13C), [M(OC6H2 But3-2,4,6)2]2, (M = Ca, Sr, Ba; 13C), [Ba2(OSiBu3)4 (THF)] (13C), [Ba(dpm)2(OEt2)]2, (13C), [Ba(dpm)2(2,5,8,11,14-pentaoxaheptadecane)], (13C), and [M(TeSi(SiMe3)3)2], (M = Mg, Ca, Sr, Ba; 125Te).
Complexes of Group 3, the Lanthanides, and Actinides. — The 31P NMR spectrum of the Y complex of 1,4,7,10-((HO)P(O)(Me) CH2)4-1,4,7,10-tetra-azacyclohexadecane shows Y coupling. 13C T1 measurements have been used to determine the structure of lanthanide complexes of oxyethylene glycols. NMR data have also been reported for [(η5-C5Me 5)2Y2(OC6H3But2-,2,6)2(µ-H)(µ-CH2CH2 CH3)], (13C), [{Y(η13-C3H5) [N(SiMe2CH2PMe2)2}]2 (µ-Cl)], (13C), [(η5-C5H5) 2Y(η5-2-Me2NC5H3-C, N) Fe(η5-C5H5)], (13C), [(η5-C5H4SiMe3)2, Y(OMe)] 2, (13C), (12), (13C), [(η5 -C5Me5)La(NHEt)(NH2Et)], (13C), [{(THF) 2Li(µ-Cl) 2}2(η5 -C5H4Me)La-(THF)], (13C), [(η5 -C5Me5)2 La(OCMe2)(OCEt=CHMe)], (13), [(η5-C5H5)(η5 -C5H4PPh2)2-La(THF)], (13C) [ScCl2(18-crown-6)]+, (13), [La(acetone isonicotinoylhydrazone)3]13+, (13C, 139La), [YCu(OSiPh3)4(PMe2Ph)], (29Si, 89Y), [(η5-C5H5)Co{P(OEt) 2 O} 3Y[(η5-C5H5) Co{P(O)(OEt) 2}2{P(O) 2(OEt)}] 2Y {OP(OEt) 2}3Co(η5-C5H5)], (13C), [La[diethylene glycol di(o-hydroxyphenyl)ether)] 3+, (13), [Ce(OCBut3)3(O2CPh)], (13C), [Ce(OPri)3(µ-OC2H4 NMeC2H4NMe2)]2, (13), [(η5-C5Me5)2Sm(THF)(N2 H4)][BPh4], (11B, 13C), [(η5-C5H5)2LuCh2 CH2CH2NMe2], (13C), [(η5-C5H5 Lu(Ch2CHMeCH2 NMe2)Cl(THF)2], (13C),[{η5 -C5H3(SiMe3)2-1,3}} 2Yb]∞, (13C, 29, 171 Yb), [{Ph2P(NSiMe3)2}2 Yb(THF) 2], (171Yb), [Yb{Al(OPri)4}2], (171Yb), [Yb(OC6H2But2- 2,6-Me-4)2(THF)3], (13C), [Y(OCPri2CH2OEt)3], (13C, Y), [Yb(TeC6 H2Me3-2,4,6)2(THF)n], (13)C, 125Te, 171Yb), [(η5-C5Me5) 2U(NPh)2], (13C), and (13), (13C).
Complexes of Group 4 — 1H NOE measurements on [(PhCH2)2Zr(η5-C5H4 But)2] show small enhancements. When the experiment is run in the presence of a polymer to increase the viscosity, there are large negative NOES to everything. NMR data have also been reported for (14), (R = H 13C), [{(η5-C5Me5)2MH}2 {µ-(CH2)5}], (M = Zr, HF; 13C), [(η5-C5H5)2Ti(CH3 (O2CR)], (13C), [(η5-C5 H5)2Ti(CH2Ph)2], (13C), [(η5-C5H5)(η5 -C5Me5)M(CH2PPh2)2], (M = Ti, Zr; 13C), [(η5-C5Me5) 2TiR1R2], (13C), [RTi(Me2 SiCH2CH2)3N], (M = Cl, Bun; 13C), [(η5-C5Me5)2 TIR1R2], (13C), [RTi(Me2SiCH2 CH2)3N], (M = Cl, Bun; 13C), (η5-C5Me5)2Ti(CMe=CHR)Cl], (13C), [(2,6-Ph2C6H3O)2 TiCEt=CEtC(H)(Ph)NCH2Ph], (13C), [(η5 -C5H5)2Ti(PMe3)=C=C=Ti(PMe3) (η5-C5H5)2], (13C), [(η5-C5H5)Ti(C[equivalent to]CSiMe3)] 2, (13C), [(η5-C5H4SiMe3) 2Ti(C[equivalent to]CPh-η2)2Ni(CO)], (13C) [(η5-C5H5)2Zr(η2 -CMeNBut)(µ-O,O'-O2CHCF3)ZrMe (η5-C5H5)2],(13C), [(η5-C5H5)4Zr2(µ -CH3)(µ-C=CMeR)]+, (13C), [(η5-C5H5)2Zr(µ-η1: η2-PhC[equivalent to]CPh) (µ-CH3)AlMe2], (13C), (14), (R = Me; 13C), [(η5-C5 H5)4Zr2Et2(µ-C=CCMe2)], (13C), (15), (13C), [{(η5-C5 H5)2EtZrOCH2}2CHOZrEt [(η5-C5H5)2], (13C), (16), (13C), (17), (13C), [(η5-C5 H5)2Zr{CH(Me)(6-ethylpyrid-2-yl)} (CO)]+, (13C), [rac-C2H4(indenyl-η5) 2Zr{CH(SiMe2Cl)(SiMe3)}][Al2 Cl6.5Me0.5], (13C), [(η5 -C5H5)2ZrClC(NBut)C[equivalent to] Cru(η5-C5H5)(PMe3)2], (13C), (18), (13C), (η5-C5 Me5)2Zr{Sn[CH(SiMe3)2]2} 2], (13C), Sn), (19), (13C), [(η5 -C5Me5)2Zr(CH=CRC[equivalent to]CR)] +, (13C), [(η5-C5H5) 2ZrSGeMe2-2-C6H4], (13C), [(η5-C5H5)2Zr(2-C4 H3E)2], (E = O, S; (13C), [{(η5 -C5H5)Zr(µ-C[equivalent to]CPh)}2 (µ-η5,η5-C10H8)], (13C), [(η5-C5H5) (η5-C5Me5)Hf(SiH2Ph)Cl], (13C, 29Si), [(η5-C5H5) (η5-C5Me5)Hf{Si(SiMe3)3} Me], (13C, 29Si).
(Continues...)
Excerpted from Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 26 by G. Davidson. Copyright © 1993 The Royal Society of Chemistry. Excerpted by permission of The Royal Society of Chemistry.
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§ 5 Choice of law, place of fulfilment, jurisdiction
(1) German law shall apply. This choice of law only applies to customers if it does not result in the revocation of the protection guaranteed by the mandatory provisions of the law of the country in which the respective customer’s usual place of residence is located (benefit-of-the-doubt principle).
(2) If you are not a consumer, but a businessman, a legal entity under public law or an institutional fund governed by public law, our place of business is the place of jurisdiction as well as the place of fulfilment for all services that follow from the business relationships that exist with us. The same condition applies to situations in which you are not associated with a general place of jurisdiction in Germany or the EU, as well as situations in which the place of residence or the usual place of residence is not known at the time of commencement of proceedings. This has no bearing on the capacity to call upon the court associated with another place of jurisdiction.
(3) The provisions of the UN Convention on Contracts for the International Sale of Goods are explicitly inapplicable.
II. Customer information
- Identity of the seller
Moluna GmbH
Engberdingdamm 27
48268 Greven
Germany
Telephone: 02571/5698933
E-Mail: abe@moluna.de
- Information regarding the conclusion of the contract
The technical steps associated with the conclusion of the contract, the contract conclusion itself and the correction options are executed in accordance to the regulations "conclusion of the contract" in our standard business terms (part I.).
- Contractual language, saving the text of the contract
3.1 Contract language shall be English.
3.2 The complete text of the contract is not saved with us. Before the order is sent, the contract data can be printed out or electronically saved using the browser’s print function. After the order is received by us, the order data, the legally-mandated details related to distance selling contracts and the standard business terms are re-sent to you via e-mail.
- Main features of the product or service
The key features of the goods and/or services can be found in the respective quote.
- Prices and payment arrangements
5.1 The prices mentioned in the respective offers represent total prices, as do the shipping costs. They include all the price components, including all the incidental taxes.
5.2 The dispatch costs that are incurred are not included in the purchase price. They can be viewed by clicking the appropriate button on our website or in the respective quote, are shown separately over the course of the order transaction and must additionally be borne by you, insofar as free delivery is not confirmed.
5.3 The payment methods that are available to you are shown by clicking the appropriate button on our website or are disclosed in the respective quote.
5.4 Unless otherwise specified for the respective payment methods, the payment claims arising from the contract that has been concluded become payable immediately.
- Delivery conditions
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