Abstract
A synthetic route to a new type of phosphinine-based macrocycle has been developed. This approach involves the reaction of a phosphinine bearing two pendant SiMe2OSiMe2CCR (R = Ph) (5) groups with two equivalents of a diazaphosphinine (1). The 2,6-bis(azaphosphininedimethylsilyl)phosphinine (6) formed was then reacted under dilute conditions with a second equivalent of phosphinine 5 to produce the new macrocycle 4. The X-ray crystal structure of 4 reveals no particular strain, and the macrocycle was fluxional in solution even at low temperature (−60 °C). Reactions of macrocycle 4 with [Cu(MeCN)4][BF4], [Ag][BF4] and [AuCl(SMe2)] in the presence of GaCl3 as chloride abstractor yielded the corresponding cationic complexes 8, 9, and 10. The X-ray crystal structure of the copper complex 8 was recorded. As expected, the overall geometry around copper is trigonal planar. The macrocycle adopts a distorted arrangement to accommodate this geometry, and the phosphinines do not bind copper in a linear fashion. The examination of metric parameters suggests that the aromaticity of the rings has not been perturbed due to a weak bonding between phosphorus atoms and copper. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)
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