Spectroscopic Properties of Inorganic and Organometallic Compounds: Volume 39 (Specialist Periodical Reports, Band 39) - Hardcover

Hardcover

ISBN 10: 0854044566 ISBN 13: 9780854044566

Verlag: Royal Society of Chemistry, 2007

Inhaltsangabe

This series provides an unequalled source of information on an area of chemistry that continues to grow in importance. 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 the field, researchers will find this an invaluable source of information on current methods and applications. Volume 39 provides a critical review of the literature published up to late 2004.

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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.

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Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 39

A Review of the Literature Published up to Late 2005

By G. Davidson

The Royal Society of Chemistry

Copyright © 2007 The Royal Society of Chemistry
All rights reserved.

ISBN: 978-0-85404-456-6

Contents

Preface G. Davidson, 7, 
NMR spectroscopy in the liquid and gas phases G. Davidson, 15, 
Solid state NMR spectroscopy G. Davidson, 136, 
Nuclear quadrupole resonance spectroscopy K. B. Dillon, 187, 
Characteristic vibrations of compounds of main group elements G. Davidson, 197, 
Vibrational spectra of transition element compounds G. Davidson, 259, 
Vibrational spectra of some co-ordinated ligands G. Davidson, 301, 
Gas-phase molecular structures determined by electron diffraction D. W. H. Rankin and H. E. Robertson, 355, 

CHAPTER 1

NMR spectroscopy in the liquid and gas phases

G. Davidson DOI: 10.1039/b601316n

1. Introduction

The format of this chapter is the same as for last year, with the emphasis on studies where NMR results have made a significant contribution to structural or other conclusions.

2. Stereochemistry

2.1 Compounds of group 1

1H, 7Li and 19F NMR PGSE experiments were used to characterise anion/cation interactions in a range of salts, including Li+BF4-, [K(18-crown-6)] + (NPh2)-. A 7Li NMR study has been made of the phase diagram for Li–T1 alloys. 1H, 6Li and 13C NMR data were used to determine the structures of aggregates found in mixtures of MeLi and LiX (X = Br or I) in Et2OH or thf solutions.

The complexation of Li+ by three chromoionophoric calix[4]arenes was studied using 1H and 7Li NMR spectroscopy. 1H, 6Li and 13C NMR spectra were used to characterise organo-lithium hetero-aggregates, Li4Ar2 (nBu) 2, where Ar = C6H4CH(Me)NMe2-2. 1H and 7Li NMR experiments (1H NOESY, TOCSY; 1H/7Li HSQC etc.) on the solution structure of (1) showed the presence of monomers, dimers and tetramers. 6Li NMR data were used to probe solvent effects on aggregates of 3-amino-pyrrolidine lithium amides and alkyl -lithiums.

7Li NMR spectroscopy was able to identify the Li+ binding sites in phospholipids, e.g.human neuroblastoma SH-SY5Y cells. The dimeric trilithium β -diketiminate [Li3 (L)(tmen)], where L = N(SiMe3)C(R)CHCl(R)N((SiMe3), R = C6H4tBu-4, gives 6,7Li NMR spectra consistent with the dimeric, 'cis-like' structure (2).

NMR spectra (13C, 29Si, 119Sn) were obtained for (Me33Si) 3SnM+, where M = Li, Na, K, Rb or Cs. At low temperatures, 7Li/119Sn coupling was seen between [(Me3Si)3Sn]- and [Li(thf)3]+ or [Li(12C4)] +.

A +H NMR study has been made of the structures of the ditopic macrobicyclic receptor + M+A-, (3), where MA = LiNO3, NaNO3, KNO3, NaNO2, KOAc. 1H, 7Li, 13C and 23Na NMR experiments were made to characterise complexes of oligomycin A with Li+ and Na+ cations. The 1H, 7Li, 13C and 31P NMR spectra of [{(LiCH2PPh2=NPh) · (LiOC6H2-2,6-tBu2-4- CH3)] 2 shows that the solution structure is a six-rung ladder, with 2 LiPCN units fused to a central Li2O2 core.

DFT calculations have been made of 13C NMR spectra of Li+, Na+ and Mg2+ coordination complexes with acetylacetone. 1H and 19F NMR spectra were used to characterise F3CSO2N(Li)SO2(CF2)x- SO2N(Li)SO2CF3, where x= 2, 4, 6, or 8. 7Li NMR images were reported for molten LiCl at 700°C.

23Na NMR micro-imaging was used to monitor NaCl distribution in living plants. NMR data (1H, 13C, 29Si) were obtained for M(donor)nGe(SiMe3)3, where M = K, Rb, donor = 18-crown-6, n= 1; M = K, donor = tmeda, n= 2, 6. An ab initio calculation has been made of NMR data for alkali-doped fullerides, especially CsC60.

NMR data have also been reported for Li[C2F5BF3] (1H, 7Li, 11B, 19F); (C6F5)2Li and its dimeric solvates with Et2O or thf (1H, 13C{1H}, 19F); [(L)M{(nPr2P)2CCH2}]2, where (L)M = (thf) 2 Li, (thf)3Na, (dme)2K (1H, 13C, 31P); (4) and related species (1H, 13C, 31P); Ar2Li4 Bu2, where Ar = C6H4CH(NMe2)CH3 (1H, 6Li, 13C); (5) (1H, 13C); (6) and related compounds (15N, 13P); Li+Im(BF3) 2- and related (Im = imidazole) (1H, 11B, 19F); M[(SPPh2)(O2SR)N], where M = Li, Na, or K, R = Me, 4-MeC6H4 (1H, 13C, 31P); [tBu2AlCH2NiPr2 · LiCl] 2 (1H, 7Li, 13C, 27Al); [NaPb(ClO4)(en)(NO2)2] 2n (1H, 13C, 207Pb); [(LiCl)6{(Me2NCH2C8H5N) 3P}2] (1H, 13C, 31P);31 [K(18-crown-6)] +[RNSN]-, where R = adamantyl, tBu,Me3Si, Ph, 4-FC6H4) (1H, 13C, 14N, 19F, 29Si, 39K).

2.2 Compounds of group 2

The structure of (NH4)6 [Be2Al2 (citrate)4] was determined using 9Be and 27Al NMR spectroscopy.

The 11B NMR spectra of [(RO)Mg(BH4)(OEt2)] 2, where R = iPr, tBu, tBuCH2, Etv3C or Me3Si, show that hydrogen atoms of the BH4 group are magnetically equivalent with respect to the Mg2O2 ring unit. The 1H, 13C and 11B NMR spectra of (7), where R = tBu, mes, L = none; R = Me, L = OEt2etc., Dipp = di-isopropylphenyl, show that all adopt a distorted boat conformation with a transannular Mg–N interaction.

1H NMR relaxation measurements have been reported for bacteriochlorophyll c in solution. A 1H NMR study has been made of Mg2+ binding properties of a conserved 75mer RNA motif of the EMCV picornavirus IRES element. DFT calculations have been made of the 1H and 13C chemical shifts for magnesium aspartate-arginine, [Mg(Asp–Arg)]. 1H and 31P NMR data were reported for a magnesium porphyrinazate containing eight [triphenyl -(2-sulfonyl-ethoxycarbonyl- 2-propyl)phosphonium]bromide groups.

1H and 13C NMR measurements on Cp2Ba(18-crown-6) show axial Cp ligands and an equatorial 18-crown-6 ligand at the central Ba2+. The 1H and 13C{1H} NMR spectra of [(η5-LiPr)Ba(µ-η 5:η5-LiPr)(µ-η 1:η1-L iPrBa(η5-LiPr), where HLiPr = (8), show that the dinuclear structure persists in solution. Similar data for BA(L)(NCS)2, where L = (9), show that the Ba2+ is coordinated unsymmetrically in the ring cavity of L.

Other NMR studies were reported for: MgMeBe(pmdta), where pmdta = N, N, N', N'" N"'- pentamethyldiethylenetriamine (1H, 13C); alkylmagnesium amides, e.g.tBuMg(DBA), where DBA = dibenzylamide (1H, 13C); M{N(2,4,6-Me3C6H 2) (SiMe3)}}2 (thf) 2, M = Mg, Ca, Sr, Ba (1H, 13C); [(ArHN)M{µ 3-N)(m3NH) 2Ti3) (η 5-C5Me5)(µ 3-N)}]n, M = Mg, Ca (1H, 13C{1H}); (bph-BIAN)M(L)2, where bph- BIAN = 1,2-bis[(2-biphenyl)imino] acenaphthene, M = Mg, L = dme; M = Ca, L = thf (1H, 13C); Ca[N(R)(SiMe3)] 2 (solv) x, where R = SiMe2tBu, SiPh2tBu, SiPh3 (1H, 13C); (10), E = P, CH, L = dme (13C, 31P); [{([Me 3Si]2CH)(C6H4-2-OMe)P}2 M(thf)n], M = Sr, n= 2; M = Ba, n= 3, and related species (1H, 13C, 31P{1H}).

2.3 Compounds of group 3 (scandium, yttrium, lanthanides, actinides)

The 1H and 13C NMR spectra of the fulleropyrrolidine derivative of Sc3N@C80 show that substitution has occurred at the [5,6]-double bond of the cage. The low-temperature 1H and 19F NMR spectra of (11) are consistent with the presence of two diastereoisomers, in which C6F5 occupies endo or exopositions. The 1H and 13C{1H} NMR spectra of MCl2 (κ3-L)(thf),where M = Sc or Y, L = (12), R = COOH, CSSH, CH2OH, show that the pyrazole rings are equivalent in all cases. 45Sc NMR spectra were used to characterise hydrogen-bonded aggregates in Sc3+– Cl-–H2O-organic solvent systems.

Variable-temperature 1H and...

Details zur Ausgabe

• Verlag: Royal Society of Chemistry
• Erscheinungsdatum: 2007
• Sprache: Englisch
• ISBN 10: 0854044566
• ISBN 13: 9780854044566
• Einband: Gebundene Ausgabe
• Anzahl der Seiten: 382
• Herausgeber: Davidson G.
• Kontakt zum Hersteller: Nicht verfügbar
• Verantwortliche Person: Nicht verfügbar