ISSN:
0009-2940
Keywords:
[2.2.2]Paracyclophane ligand
;
(η6)π Complexes
;
Arsenic(III) complexes
;
Antimony(III) complexes
;
Bismuth(III) complexes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Arsenic(III), Antimony(III), and Bismuth(III) Trihalide Complexes of [2.2.2]Paracyclophane: From Weak van der Waals Coordination to Strongly Directional π Complexation with Single or Double External η6 Coordination[2.2.2]Paracyclophane forms the adducts C24H24·AsCl3 (1), C24H24·(SbCl3)2·1/2 C6H6 (2), and C24H24·(BiCl3)3·C6H6 (3). For solutions in polar solvents NMR spectra indicate extensive dissociation and/or fluxionality. In the crystals adduct 1 features a weak addition of the AsCl3 molecule to one open side of a paracyclophane molecule with long intermolecular contacts approaching C3v symmetry. - Crystalline 2 shows SbCl3 coordination to two of the benzene rings of the hydrocarbon in a quasi-centered η6 mode, while one of the benzene rings remains uncoordinated. Chlorine-bridging between antimony atoms leads to tetrameric units (SbCI3)4 in the lattice. - In the bismuth compound 3 each benzene ring of the hydrocarbon is engaged in centroid (η6)π complexation, with the BiCl3 units crosslinked by chlorine bridges. The average of the Bi-ring distances (3.08,2.98, and 2.99 Å) is shorter than for the Sb-ring distances in 2 (3.047 and 3.050 Å), indicating stronger bonding. The crystal benzene is not coordinating.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19911240516
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