Conformational behavior of tris(pentafluorophenyl)borane-benzotriazole adducts

Organometallics

Volumn 25, Issue 9, 2006, Pages 2166-2172

  Focante, Francesca ^a,c   Leardini, Rino ^a   Mazzanti, Andrea ^a   Mercandelli, Pierluigi ^b   Nanni, Daniele ^a  

^a UNIVERSITY OF BOLOGNA   (Italy)

^b UNIVERSITY OF MILAN   (Italy)

^c Basell Polyolefins   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

CRYSTALLINE MATERIALS; ISOMERS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; X RAY CRYSTALLOGRAPHY;

ENANTIOMERIZATION; ENANTIOMERS; TRIS(PENTAFLUOROPHENYL)BORANE-BENZOTRIAZOLE ADDUCTS;

ORGANOMETALLICS;

EID: 33646433719     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om051003t     Document Type: Article

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44. 45 are related to the B-N rotation process and they exchange the first with the sixth line and the fourth with the fifth, respectively.
45. The other possibility, i.e., a one-ring flip between A and B, would require a transition state in which ring A is orthogonal to the benzotriazole ring; this would imply the exchange between the two ortho fluorine signals of ring A, in contrast with the experimental evidence.
46. Due to the huge molecular complexity, we did not attempt to calculate the full equilibration pathway for compound 1. Therefore we could not completely exclude the possibility of a single concerted transition state for the enantiomerization process. In this case, however, the transition state would also correspond to the passage of one ortho fluorine of ring A over the benzotriazole.
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49. Mean bond distances (Å) for the benzotriazolato ligand are as follows: N-N 1.334, N-C 1.366, C(3a)-C(7a) 1.393, C(3a)-C(4) 1.405, C(4)-C(5) 1.368, C(5)-C(6) 1.407.
50. 2 relaxation induced by the quadrupolar effect of the two boron atoms. This broadening is much less marked when only one boron atom is present, like in 1 and 2.
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