Charge distribution in substituted cyclopentadienyl–manganese–tricarbonyl compounds

1967 ◽  
Vol 45 (2) ◽  
pp. 161-166 ◽  
Author(s):  
C. Barbeau

Photochemical synthesis of mono- and bi-substituted cyclopentadienyl–manganese–tricarbonyl compounds with triphenyl-phosphine, arsine, stibine, and bismuth is reported. The infrared absorption and proton magnetic resonance spectra are discussed in relation to the distribution of negative charges among the ligands. The dipole moments were measured and the partial dipole moments for the group manganese–triphenyl compound in these derivatives are calculated and discussed.It is shown that the distribution of negative charges occurs principally between the CO and phenyl ligands and that the donor–acceptor behavior of the phenyl ligands depends mainly on the phenyl group and to a very small extent on the central atom.

1968 ◽  
Vol 46 (14) ◽  
pp. 2373-2384 ◽  
Author(s):  
Seán Cawley ◽  
Steven S. Danyluk

A study has been made of the proton magnetic resonance spectra for all of the Group IVB derivatives of the series MVi4 and [Formula: see text]([Formula: see text] = phenyl group and Vi = vinyl group). The spectra were measured at 60 MHz as accurately as possible and the assignment of transitions was checked with a variety of supplemental aids including double irradiation, multiple quantum transitions, and medium effects Final, accurate spectral parameters were derived using both iterative and exact computational methods for solution of the three-spin problem Excellent agreement was obtained between the sets of parameters determined by the two methodsThe chemical shifts for both series of compounds display a number of characteristic trends of which the most notable is a displacement of the vinyl proton signals to low field with increasing atomic number of the M atom In each series the largest shift change is noted in going from the carbon to the silicon derivative These deshieldings have been attributed to the enhanced possibility of dπ–pπ interaction between the central M atom and the vinyl group in higher members of the series Marked changes are also the internal shifts of the vinyl protons down both series of compounds It is concluded that these changes are principally due to the effects of the M—C bond diamagnetic anisotropy The trends in internal shifts can be satisfactorily reproduced by the dipole approximation using Δχ values of 4, 6, 8, 12, and 18 × 10−6 cm3 mole−1 for the C, Si, Ge, Sn, and Pb–carbon bonds respectivelyThe signals for the vinyl protons of the [Formula: see text] series are all located to low field relative to the MVi4 series This deshielding is satisfactorily accounted for by the effects of the phenyl ring diamagnetic anisotropy in the former seriesA linear correlation is observed between the sums of the coupling constants and the electronegativities, Em, of the central M atom for both series of compounds However, the ΣJ values for the [Formula: see text] series are all slightly lower than the corresponding sums for the MVi4 series, indicating that the electronegativity of the phenyl group is somewhat larger than for the vinyl groupA significant solvent and concentration dependence is only noted for compounds belonging to the [Formula: see text] series For example, the trans proton of [Formula: see text] shifts up-field by 4 Hz while the cis proton is displaced down-field by 4 Hz as the concentration of [Formula: see text] is increased to 50 mole % in carbon tetrachloride These changes have been interpreted on the basis of a solute–solute interaction scheme of the type proposed previously for phenyl proton shifts.


1960 ◽  
Vol 13 (1) ◽  
pp. 38 ◽  
Author(s):  
RD Brown ◽  
ML Heffernan

Results of a variable-electronegativity SCF treatment of azulene, using the method used in previous VESCF studies, are reported. A slightly more elaborate method in which non-neighbour core resonance integrals are included has also been used. The π-electron distributions obtained by these methods correspond to dipole moments of 1.85 and 1.33 D respectively, the experimental value being about 1 D. The calculated bond orders accord with the rather incomplete experimental data on bond lengths. The π-electron densities account for the relative chemical reactivities of the azulene positions. The ionization potentials and proton magnetic resonance spectrum of azulene are also briefly considered. The concept of electronegativities of conjugated atoms in non-alternant systems is discussed in some detail on the basis of the VESCF results. It is shown that the assumption that the electronegativity of a carbon atom depends only on its π-electron density is an oversimplification for non-alternant systems.


1968 ◽  
Vol 21 (6) ◽  
pp. 1497 ◽  
Author(s):  
EA Jeffery ◽  
T Mole

The kinetics of exchange of a methyl group of trimethylaluminiunl for a phenyl group of triphenylaluminium have been studied by the use of proton magnetic resonance (p.m.r.) spectroscopy. An excess of pyridine was always present. Results obtained using a large excess support a bimolecular mechanism without loss of pyridine from the organoaluminium complexes prior to exchange. When the excess of pyridine is small, the rate of exchange depends on the concentration of excess pyridine. Here reaction may proceed by a mechanism in which loss of pyridine from one of the organoaluminium complexes occurs prior to exchange.


1968 ◽  
Vol 46 (11) ◽  
pp. 1873-1880 ◽  
Author(s):  
O. Exner ◽  
M. H. Benn ◽  
Frances Willis

The configurations and conformations of S-methyl benzothiohydroxamic acid (3) and its S-oxo and S,S-dioxo derivatives (5) and (7) were established by means of a graphical comparison of their dipole moments with those of the corresponding p-nitro compounds.The proton magnetic resonance and infrared spectra of these compounds were also studied.It is concluded that the relative stability of stereoisomers in the series of compounds C6H5C(NOH)X seems to depend more on the electronic nature of the group X than on its steric requirements.


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