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27644557032
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note
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IV coordination by a chiral phosphine. The complex was only prepared as racemate, however.
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Müller, G.1
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27644535313
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note
-
Anionic phosphines are conveniently subdivided into those having the anionic function directly attached to phosphorus, as is the case in phosphinomethanides and phosphinoamides, and into those having the anionic function more remote from phosphorus. The negative charge directly adjacent to phosphorus in phosphinomethanides and phosphinoamides considerably enhances the electron density and donor capacity of their phosphino groups, while the second type of ligands resembles more closely neutral phosphines in its donor capacity. Phosphino alcoholates generally fall into this second class of anionic phosphines.
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The refinable absolute structure parameter x may take on values between 0.0 and 1.0. If it refines to 0.0 the chirality or polarity of the refined structure corresponds to that of the crystal, if x = 1.0 refined structure and the crystal have opposite chirality/polarity. Intermediate values of x are possible. They indicate racemic twins, x = 0.5 pointing to identical twin domains. As usual, for assessing the significance of x the estimated standard deviation σ, as given in units of the last significant figure in parentheses, is crucial. If one conservatively estimates the error to be ±3 σ it becomes clear that, e. g., x = 0.0(2) does not allow to distinguish between enantiomers while x = 0.00(2) does: H. D. Flack, G. Bernardinelli, J. Appl. Cryst. 2000, 33, 1143;
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53
-
-
27644447900
-
-
note
-
Alternatively, the structure may be described as a tetrahedron of lithium atoms with the oxygen atoms capping the tetrahedral faces. We prefer the description as heterocubane, however, as this reflects more the actual bonding interactions between lithium and oxygen.
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54
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18444416289
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55
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0005411482
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56
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61
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27644471018
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note
-
Similar experiments were not possible for 5, as this compound could not be subjected to chiral HPLC, as described above.
-
-
-
-
62
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27644485031
-
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note
-
The same applies for the structure of 5-rac not shown in this paper.
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