Hyperfine splitting of the odd 4 F J o , 2 P J o and 4 S J o LaI multiplets

High resolution spectra of LaI lines recorded in the R6G region by laser-induced resonance fluorescence method show well resolved hyperfine structures. The analysis of the hyperfine structure of seven LaI transitions is presented here. It has allowed the deduction of magnetic dipole and electric quadrupole constants of all levels belonging to the excited odd parity multiplets: ⁴ F ^o (J = 3/2-9/2), ² P ^o (J = 1/2,3/2), and ⁴ S ^o (J = 3/2). Some of the results are new and some of them present improved values of the hyperfine splitting constants.     

Experimental separation of torsional and charge redistribution effects in rotational spectra of HCN dimers

B_oand D^jhave been determined for H¹³C¹⁵N-HC¹⁵N, HC¹⁵N-H¹³C¹⁵N, HC¹⁵N-DC¹⁴N and DC¹³N-HC¹⁵N. From them and other, previous results a full substitution structure has been obtained for HCN(1)-HCN(2). It leads to torsional amplitudes θ₁ and θ₂ of 13.6 and 9.3° for the two monomers in the dimer. A determination by fitting B_o for six isotopic species gives 13.7 and 8.7°. These values are used to separate torsional and charge redistribution effects upon the hyperfine interactions of ¹⁴N and D in the dimers. For ¹⁴N, about 40% of the difference in χ_a between HCN monomer and dimer is caused by charge redistribution. The C-D bond length in the dimer is considered.     

Study of electron spin crossover in iron(III) tris-dithiocarbamate complexes by carbon-13 NMR spectroscopy

¹³C and ¹H isotropic shifts have been measured for a series of Fe(III) tris-dithiocarbamate complexes. The ¹³C isotropic shifts may be interpreted as arising solely from contact hyperfine coupling and demonstrate that as the low-spin state of the metal is favoured there is an increase in metal-ligand π-bonding. σ-delocalization of unpaired spin density is more important in determining the ¹³C isotropic shifts than those of the contiguous proton.     

Large-scale MCHF calculations of hyperfine structures in nitrogen and oxygen

The hyperfine structure constants for the 1s ²2s ²2p ³ -⁴ S ^o ground state in nitrogen and the 1s ²2s ²2p ³3s ⁵ S ^o excited state in oxygen are calculated using the MCHF Atomic Structure Package. The single excitation picture is explored through the use of compact wave functions allowing radial non-orthogonalities. Electron correlation is described through numerical multiconfiguration Hartree-Fock calculations for configuration expansions obtained by allowing all single and double excitations from the reference configuration to an active set of orbitals. The latter is increased in a systematic way allowing the convergence of the hyperfine parameters to be studied. Three- and four-particle effects are shown to be important and are taken into account in a sequence of large configuration interaction calculations. The final results are in good agreement with experiment.     

1H and 13C endor on phenoxyl biradicals randomly oriented in frozen solution

ENDOR measurements have been performed on ¹³C labelled biradicals, namely Yang's biradical and p-phenylenebisgalvinoxyl, in frozen solutions. Besides intense ENDOR lines at the free nuclear Zeeman frequencies, hyperfine shifted ¹H and ¹³ ENDOR lines could be detected with excellent signal-to-noise ratios. From these spectra not only the magnitudes, but also the signs of the hyperfine splitting components relative to the zero field splitting parameter D could be derived. It is demonstrated that the sign of D in Yang's biradical must be negative. This may be due to a spin-orbit coupling contribution to the zero field splitting parameter.     

Electric dipole moment of the diatomic AgBr molecule

Stark effect measurements on hyperfine components of the J = 3 – 2 rotational transition of ¹⁰⁷ Ag ⁷⁹ Br and ¹⁰⁹ Ag⁷⁹ Br at 11.5 GHz were carried out. The electric dipole moment derived for AgBr in its ground electronic and vibrational state is |μ_o| = 5.620 ± 0.030 D.     

High-resolution solid-state 11B and 13C MAS NMR of icosahedral carboranes

The globular-shaped icosahedral carboranes, o-, m-, and p-C₂B₁₀H₁₂, yield high-resolution ¹¹B and ¹³C MAS solid-state NMR spectra. Chemical shifts and linewidths are comparable to those of solution spectra. Spin—lattice relaxation times indicate the quadrupolar mechanism to be dominant for the B-11 relaxation. Linewidths of spectra recorded at 96 MHz and 64 MHz were similar. At 298 K, the ¹³C T₁ of p-carborane was found to be an order of magnitude smaller than those of the other two isomers. This can be attributed to the higher phase transition temperature of p-carborane indicative of the stronger intermolecular dipolar CH interactions made possible by the para-carbon vertices. Substitution on o-carborane by a methyl group yields spectra of comparable linewidths to those of the parent compound. Substitution by a bulkier phenyl group, however, results in extensive broadening of both ¹¹B and 13C signals of the derivative 1-Ph-o-C₂B₁₀H₁₁.     

The t-butyl group as sensor group of the ortho effect

The ¹³C chemical shift difference between the Me group C atoms and the quaternary C atom of the t-Bu group in 58 p-, m- and o-substituted t-butyl-benzenes has been measured and analysed in terms of inductive. mesomeric and proximity effects. It is shown that the ortho effect is too complex to justify a unified explanation by a correlation treatment.     

Hyperfine structure in the configurations 4f 13 6s6p and 4f 125d6s 2 of TmI

The laser-atomic-beam spectroscopy has been used to make precise measurements of the hyperfine structure in transitions starting from metastable states of the configuration 4f ¹²5d6s ² in¹⁶⁹TmI. With the resulting experimental magnetic dipole hyperfine constantsA _J andA _J values from former investigations a parametric analysis of the hyperfine structure in the configurations 4f ¹³6s6p and 4f ¹²5d6s ² has been performed using wavefunctions from fine structure calculations. A comparison of theoretical and experimental hyperfine constants allowed a test of the reliability of the wave-functions used. The hyperfine parameters respectively hyperfine radial integrals determined from the analysis were compared with corresponding data from ab initio calculations for the ground configuration in TmI.     

The reaction of aqua-(ethylenediaminetetra-acetato)ruthenium(III) with o-phenylenediamine under aerobic conditions

An electron-transfer reaction between [Ru(III)(Hedta)(H₂O)] and o-phenylenediamine in the presence of O₂ takes place to give a Ru(II)-edta complex with coordinated (bidentate) o-benzoquinone diimine. The complex obtained has been characterized by analysis, magnetic measurements, electronic, IR, ¹H and ¹³C NMR spectral data.     

The hyperfine structure in the configuration 4f 135d6s6p in ytterbium

Using Doppler-reduced laser induced fluorescence spectroscopy in an atomic beam, the hyperfine structure of 22 levels of the configuration 4f ¹³5d6s6p in neutral ytterbium has been investigated for the two odd isotopes ¹⁷¹ Yb and ¹⁷¹ Yb. The experimental results have been used in a study of the hyperfine structure in regard to a determination of the one-electron parameters for the magnetic dipole and the electric quadrupole hyperfine coupling of the isotope ¹⁷³ Yb in part II of this work.     

Hyperfine shifts of the 13C-NMR. in low spin iron(3) porphyrin complexes

The ¹³C-NMR. in Zn(II)(Porphin), Fe(III)(Porphin)(CN₂), Zn(II)(Tetraphenyl-porphin), and Fe(III)(Tetraphenylporphin)(CN₂) have been identified, and the ¹³C hyperfine shifts in the iron complexes evaluated. It was found that dipole-dipole coupling with the electron spin localized in the π-orbitals of the aromatic carbon atoms makes an important contribution, to the ¹³C hyperfine shifts. In a preliminary analysis the experimental spin density distribution obtained from the combined ¹H- and ¹³C-NMR.-data is compared with theoretical models of the iron porphyrin complexes.     

ESR study of the radical (C6D5)313C produced in a single crystal matrix

The (C₆D₅)₃¹³C radical is produced by the x-irradiation of a single crystal of (C₆D₅)₃¹³C-H. The principal values of the hyperfine coupling with the ¹³C in the methyl position are determined as T₁ = 168 MHz, T₂ = 24 MHz, T₃= 19 MHz. The corresponding spin density is compared with the values obtained in solution by earlier authors. The principal directions are consistent with crystalline structure and show that only one of the two molecules forming the asymmetric unit is broken during irradiation.     

Stable organomercury compounds containing an o-iminosemiquinone radical ligand

A series of stable paramagnetic organomercury compounds containing the 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzosemiquinone ligand (imSQ) with the general formula imSQHgR (R = Ph, Et, Prⁿ, Buⁿ, Prⁱ, Hex^c, CH₂SiMe₃, p-FPh, Fc, p-Me₂NPh) were synthesized. The molecular and electronic structures of the synthesized compounds were investigated by EPR spectroscopy and X-ray diffraction. The o-iminosemiquinone ligand shows the unusual amidophenoxy-type coordination mode. In the EPR spectra of the compounds imSQHgR, the hyperfine coupling constant of magnetic mercury isotopes (^199,201Hg) depends on the nature of the substituent R, the temperature, and the nature of the solvent. Voltammetric investigations showed that the complex imSQHgFc undergoes three reversible one-electron redox steps related to the redox transformations of both the o-iminoquinone ligand and the metallocene moiety of the molecule.     

2-Nitromethyl-2-trichloromethyl-1,3-benzodioxoles and 2-nitromethyl-2-trichloromethyl-1,3-benzoxazolines: Synthesis and structure

A reaction of 1-bromo-3,3,3-trichloro-1-nitropropene with pyrocatechol, o-aminophenol, and their substituted derivatives led to 2-nitromethyl-2-trichloromethyl-1,3-benzodioxoles and 2-nitromethyl-2-trichloromethyl-1,3-benzoxazolines. The structure of the compounds synthesized was established by IR, ¹H and ¹³C NMR spectroscopy with HMQC and HMBC ¹H—¹³C experiments, and X-ray diffraction analysis.     

Conformational study of tetramethyl-N,N′-bis-arylcyclodisilazanes by 13C NMR and x-ray diffraction analysis: III. The conformation of tetramethyl-N,N′-bis(O-methoxyphenyl)cyclodisilazane

The conformation of tetramethyl-N,N′-bis(o-methoxyphenyl)cyclodisilazane was investigated by ¹³C NMR in solution and by X-ray diffraction in the solid state. The conformation in solution compares to that of o-methoxyaniline. The phenyl and the cyclodisilazane ring forms a dihedral angle of 7.4° and there is a non-bonded Si ⋯ O distance of 2.73 Å in the crystal. The molecular geometry suggests an analogy to S ⋯ O non-bonded interactions often observed in organosulphur chemistry.     

Carbon-13 NMR studies of some paramagnetic transition-metal acetylacetonates some linewidth considerations

Carbon 13 isotropic shifts and linewidths have been measured for a series of paramagnetic transition-metal acetylacetonates. The results have been compared with the corresponding NMR parameters of the contiguous protons. The relaxation pathway of the ¹³C spins is controlled by hyperfine interactions with the unpaired electron spins and, in cases where the proton linewidth is also dominated by the hyperfine mechanism, good agreement is obtained between the experimental ¹³C/¹H linewidth ratio and that calculated on the basis of the contact shifts. Pseudocontact interactions can be important in determining the total isotropic shift for both the ¹³C and ¹H nuclei and contrary to previous studies, it is suggested that such effects are also important for V(III) and Mn(III) acetylacetonate.     

The synthesis and characterization of telluranthrene

The reaction between o-phenylenemercury and finely powdered tellurium metal at temperatures not exceeding 250°C yields a pale yellow crystalline solid. Characterization of this solid by elemental analysis, determination of the molecular mass, mass spectral analysis, and ¹³C and ¹²⁵Te NMR spectral analysis indicates that it is the hitherto uncharacterized telluranthrene.     

Factors affecting stability and equilibria of free radicals—IX: Non-equivalence of aryl groups in 1,1-diaryl-2-benzenesulphonyl-hydrazyls and related compounds

1,1-Bis-(3',5'-di-t-butylphenyl)-2-benzenesulphonyl-hydrazine 11 and the corresponding 2-picryl-hydrazine 13 were synthesized. Oxidation of 11 afforded the stable hydrazyl 12 whose ESR spectrum could be simulated in terms of three hyperfine coupling constants. These experimental data leave no alternative but to assign larger proton hyperfine coupling constants to one aryl group in 12 than to the other. This non-equivalence was interpreted in terms of the Linnett theory. The picrylhydrazyl 14 does not give completely resolved ESR spectra. Structures were ascertained by IR, UV-vis, ¹H NMR and ¹³C NMR spectra.     

Synthesis and spectral characterization of some complexes of platinum(II) containing η-methyleugenol

Several complexes of the formula trans-[Pt(Meug)(Am)Cl₂], Meug: methyleugenol (4-allyl-1,2-dimethoxybenzene), a η²-coordinated olefin, and Am: ammine, methylamine, diethylamine, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine and p-anisidine have been prepared. UV, IR, Raman, ¹H NMR, ¹³C NMR and 2D NMR spectra of the complexes were recorded and analyzed.