Spectroscopic Properties of Inorganic and Organometallic Compounds

Spectroscopic Properties of Inorganic and Organometallic Compounds

by G Davidson (Editor)


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Spectroscopic Properties of Inorganic and Organometallic Compounds by G Davidson, Royal Society of Chemistry

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.

Product Details

ISBN-13: 9780851862439
Publisher: Royal Society of Chemistry, The
Publication date: 12/31/1992
Series: Specialist Periodical Reports Series , #25
Pages: 472
Product dimensions: 5.43(w) x 8.50(h) x (d)

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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


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 13C NMR spectra for [(C5Me4)SiMe2 (CH2CHQ CH2)] 2Y(C3H5) gave evidence for Y-alkene interaction. 1H, 13C and HMQC spectra were reported for the derivative of Y3N@C 60 with N-ethylazomethinylide. The 13C NMR spectrum of the stable diamagnetic anion Y@C82- gave evidence as to the cage structure. One- and two-dimensional 19F NMR spectroscopy was used to elucidate the structures of two isomers of the diamagnetic complex Y@C82 (CF3)5.

1H and 31P{1H} NMR data were reported for (13). The 1H NMR spectra of the complexes M(DTPA-BA2), where M = Y or In, DTPA-BA2 = N, N"-bis(benzyl- carbamoylmethyl)diethylenetriamine-N,N',N" -triacetate, show the presence of at least 3 isomers in each case.

1H and 89Y NMR spectra were used to characterise [Y4 (µ 3-η 2-OR)3 µ, η2-OR) 2 (η1-OR) 4-(µ, η1-OR)3], where R = C2H4OiPr. 1H and 13C solution NMR data show significant differences in structure and molecular dynamics for Y(III) and Ga(III) complexes of DOTATOC (a disulfide-bridged octapeptide). High-temperature NMR studies were carried out on molten YF3–LiF (7Li, 19F) and LaF3–LiF (19F, 139La), giving evidence on structural changes with composition.

13C NMR was used to identify the new metallofullerene La@C74(C6H3Cl2). Two-dimensional INADEQUATE 13C NMR spectroscopy was able to establish mapping of bond connectivity for [La@C82]-. Metal (La(III), Ti(IV), Zr(IV), Hf(IV)) complexes containing 1,2-phenylenedioxoborylcyclopentadienyl groups were studied using 1H, 11B, 13C, 29Si and 119Sn NMR spectroscopy.

NMR data (1H, 13C, 11B) were reported for {[η 5-1-La(thf) 2-2,4-(Me3Si2-2.4 -C2B4H4] 4 (µ-Cl) 2(µ4-O)} · y(thf). The 1H NMR spectrum of La(tpzcn)I3, where tpzcn = (14), is consistent with a rigid solution species on the NMR time scale. The dimeric nature of the La(III) complex of tris(salicylideneamino)triethylenetetra -mine was revealed by 1NMR spectroscopy. The 1H NMR spectra of complexes between La3+ and a bifunctional ligand containing two pyridine-2,6-dicarboxylate groups connected at the 4-position by an O(CH2CH2O)6 spacer show the formation of a three-dimensional structure with ring units. The 183W spectra of [Ce(H4XW17O61) 2]19- show that the anion has C2 symmetry.

The 31P and 99Tc NMR spectra of [UO2(MO)4)(dppmO2)2]+, where M = Tc or Re, confirm the presence of coordinated MO4- species in each case. NMR data were also reported for UO2L2, where HL = 1-phenyl-3-methyl-4-(2-thenoyl)-5 -pyrazolone-b-alanine (1C, 13C); and UO2 (NCO)2 [OP(NMe2) 3]2 (1H, 13C, 14N, 31P). The 14N NMR spectrum of UO2I2 [OP(NMe2)3]2 shows a resonance at –355 ppm due to the OP(NMe2)3 ligand. DFT calculations have been reported for the NMR parameters of UF6-nCl(n= 1–6).

2.4 Compounds of group 4

NMR data (1H, 13C, 31P) for Cp2Ti(PMe 3)(H)(SiR3), where R3 = MePhCl, Ph2Cl, MeCl2 or Cl3, gave evidence for an agostic interaction involving H and Si. Two-dimensional 1H and 13C NMR techniques (COSY, TOCSY, NOESY, HMBC) gave a complete assignment for 2G-{(CH2)3 [C6H3 (OMe)]O[TiCpCl2]}8. Evidence was found (1H, 13C, 1H{11B} NMR data) for an Z6-interaction between the cation and anion in [Ti{OB(mes) 2}2 (CH2Ph)][B(C6F5) 3 (CH2Ph)]. 13C and 29Si NMR spectra were able to identify weak α–agostic or β–Si–C agostic interactions in [Ti(NtBu) {Me3 [9]aneN3}R]+, where R = Me, CH2SiMe3 respectively.

Variable-temperature 1H NMR spectroscopy showed a mixture of cis,trans- and cis,cis-isomers for Ti(OIPr)2 (CH3COCHCONEt2)2 at -20 °C. Two-dimensional (NOESY) 1H NMR experiments were used to confirm the structure and assign resonances for (µ-CH2CH2-3,3'){(η5-indenyl)[1-Me2Si(tBuN)][Ti(NMe2)2]}{(η 5-indenyl) [1-Me2Si(tBuN)][Zr(NMe2)2]}. 1H and 13C NMR experiments (including HSQC, HBMC and ROESY techniques) were used to characterise Ti3 (µ3-O) (OiPr)4(µ-OiPr)3[Me2C(O)CHQC(O)CH2C(O)Me2]. The two-dimensional COSY 1H NMR spectrum of BiTi4 (sal)6 (µ-OiPr) 4 shows that the solution structure retains the asymmetry seen in the solid (sal = salicylate).

DFT calculations have been made of 49Ti NMR chemical shifts for TiX4 (X = F, Cl, Br), TiCln Me4-n (n = 0 - 3), Cp2TiX2 (X = F, Cl, Br) and Ti(CO)62. Variable-temperature 1H NMR spectroscopy was used to probe the coordination behaviour in MCl4 (R2SO2)2, where M = Ti, R = Me; M = Zr, R = Me, Ph, -(CH2)4-, and M2Cl8 (R2SO2)2, where M = Ti, R = -(CH2)4-; M = Zr, R = Et, Ph.

The 1H NMR spectrum of [LZr(CH2Ph)][B(C6F5) 3 (CH2Ph)], where H2L = (15), shows that tight ion-pairing occurs in solution. 1H and 13 C NMR spectra of (16) show that the imino nitrogen atoms are coordinated to the metal centre. Similar data for (17), where R = Me, Bz, CH2SiMe3, Ar = 2,6-xylyl, show typical resonance for iminoacyl complexes.

1H and 13C NMR spectra of (18), where R = Cl, Me or CH2Ph, reveal the presence of meso and rac isomers. The 1H NMR spectrum (including NOE experiments) for (19) showed the presence of a ZrCCNCZr 6-membered ring in the boat conformation. The variable-temperature 19F NMR spectrum of [(C5H4)SiMe2 (NtBu)]Zr(+)(µ-C4H6) B(-)(C6F5)3 shows that at 193 K 6 signals are seen, i.e. coordination of ortho-F has occurred to the electrophilic Zr centre.

The 1H and 31P{1H} NMR spectra were reported for eight-coordinate MX4(L–L)2, where M = Zr or Hf, X = Cl or Br, L–L = o-C6H4 (PMe2)2 or o-C6H4 (AsMe2)2. DFT calculations were made of 1H and 13C NMR parameters for [Zr(OH) 6]2- and [Zr(OH)5 (OCH2CH2CH3)] 2-. The coordination mode of triflate groups in (Nacnac)Zr(OTf)2(η 2-OTf), where Nacnac- = [Ar]NC(tBu) CHC(tBu)N[Ar], Ar = 2,6-[CH(CH3)2] 2C6H3, were determined by 19F COSY experiments.


Excerpted from Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 39 by G. Davidson. Copyright © 2007 The Royal Society of Chemistry. Excerpted by permission of The Royal Society of Chemistry.
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Table of Contents

Chapter 1: NMR spectroscopy in the liquid and gas phases; Chapter 2: Solid state NMR spectroscopy; Chapter 3: Nuclear quadrupole resonance spectroscopy; Chapter 4: Characteristic vibrations of compounds of main group elements; Chapter 5: Vibrational spectra of transition element compounds; Chapter 6: Vibrational spectra of some co-ordinated ligands; Chapter 7: Gas-phase molecular structures determined by electron diffraction

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