Angular parameters

Cobalt, R-a-cyanoethylbis(dimethylglyoximato)-racemization, 1,470 Cobalt, diacetatobis(methylimidazolyl)-angular parameters, 1, 59 Cobalt, diamminebis(dimethylglyoxime)-decomposition, 1,186 Cobalt, diamminediaquadinitroso-structure, 1,26... 

Cobalt, dinitratobis(trimethylphosphine oxide)-angular parameters, 1,57 structure, 1, 57... 

Iron, dicarbonylbis(hexahydrodithiopyridine-carboxylato)-angular parameters, I, 57 Iron, dicyanobis(2,2 -bipyridyl)-solvolysis, 1, 506... 

Molybdenum, tris(dimethyldithiocarbamato)bis-(azobenzene)-angular parameters, 1,59... 

Tin, bis(diethyldithiocarbamato)diphenyl-angular parameters, 1,57 Tin, bis(diethyldithiocarbonato)diiodo-angular parameters, 1,57 Tin, bis(diethyl dithiophosphate)diphenyl-stereochemistry, 1,59 Tin, bis(diethyldithiophosphonium)diiodo-angular parameters, 1, 57 Tin, chlorotris(tropolone)-stereochemistry, 1, 82 Tin, cyclopentadienyl-, 3, 218 Tin, dibromobis(ethyldithiocarbonato)-angular parameters, 1, 57 Tin, dichlorobis(ethyldithiocarbonato)-angular parameters, 1, 57 Tin, dimethylbis(acetylacetone)-structure, 1, 58... 

Tin, nitratodiphenyltris(dimethy) sulfoxide)-structure, 1,77 Tin, nitratotris(triphenyltin)-structure, 1, 47 Tin,tetrakis(acetato)-stereochemistry, 1,94 Tin, tetrakis(diethyldithiocarbamato)-angular parameters, 1, 57 Tin, tetrakis(ethyldithiocarbamato)-angular parameters, 1, 57 Tin, tetranitrato-stereochemistry, 1, 94 Tin, tri-n-butylmethoxy-, 3, 208 Tin alkoxides physical properties, 2, 346 Tin bromide, 3, 194 Tin bromide hydrate, 3,195 Tin carboxylates, 3, 222 mixed valence, 3, 222 Tin chloride, 3, 194 hydroformylation platinum complexes, 6, 263 Tin chloride dihydrate, 3,195 Tin complexes, 3, 183-223 acetyl ace tone... 

While it is clear that a direct measurement of the angular distribution, Eq. (4), with a given hehcity of hght should be capable of yielding the h angular parameter, it is often more convenient to examine the dichroism, or difference, obtained with opposite helicities of the light (or, possibly, of the enantiomer). From Eq. (4) and the antisymmetry property Eq. (6) one obtains an expression for the PECD ... 

Applying the symmetry condition Eq. (13) to the third CGC implies that I + l+j = even. Along with the triangle rule this requires that I = I for the isotropic term j = 0, I = l l for j = 1, and I = I 2,0 for j = 2. These deductions determine the nature of the interference implicit in each of the angular parameters The fourth CGC in Eq. (12) further regulates... 

The last two CGC in Eq. (12) evidently dictate that rather different partial wave interference contributions are made to each of the angular parameters. This will impact on the dynamical information conveyed by each one. Equally important, the phase subexpression... 

Figure 4. Calculated angular parameters p) and 1) for (S)-methyl oxirane solid...

Figure 5. Calculated angular parameters (= P) and for rmnr-(2S,3S)-difluoro-oxirane solid curves CMS-Xa broken curves B-spline (Ref. [53]). Results are given for ionization from four different orbitals (a) 11a (HOMO) (b) 9b (HOMO-1) (c) 5b (d) 3a/2b C H.

A similar convergence study has been reported for the B-spline calculation for trans-2,3 dimethyloxirane molecule, et al. [53] The authors in fact comment that the parameter is no more demanding on basis set size than the p parameter, but their data ([53] Fig. 1) show that when the asymptotic is increased from 10 to 15 there is a significantly greater improvement in the former angular parameter. A value of. (max = 15 was chosen for all subsequent B-spfine calculations for oxiranes, and the same limit tends to be applied in the other reported B-spline calculations of chiral molecule PECD [60, 61]. 

Table 10 Angular Parameters (°) of Octahedral e -[M(bidentate)2(unidentate)2] Containing Four-membered Chelate Rings...

Some of the angular parameters ( and 41) may vary slightly from values reported in the literature due to the details of the calculation, especially the location of the C3 axis (see text). 

It is less fruitful to use structural data to explain the relative rearrangement rates even for complexes which rearrange by the same mechanism. The most extensive series of constant mechanism complexes is of the M(dtc)3 type and structural results are available for many of the complexes. A comparison of AH for enantiomerization to a, 0 and 0 is made in Table 12. Although some of the AH values are within experimental error of each other, an overal relation exists. The higher AH values in general correspond to the less twisted (toward D3h) complexes, however, the magnitude of the differences in angular parameters is hardly sufficient to account... 

Dunitz and coworkers introduced two angular parameters, Xn and Xo shown in Figure 1 Xn describes a distortion of the D2 bond from the plane defined by the bonds D1 and D3, whilst Xc is a measure of D5 bond distortion from the plane defined by D1 and D4 bonds. These parameters are related to the pyramidalities of the nitrogen (Nl, sp3) and carbon (C2, sp2) atoms, respectively, and are linear combinations of pairs of the corresponding torsion angles and n ... 

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