Synthesis, structure, electronic properties and thermal behavior of butadiynyl substituted phenylCr(CO)3-complexes
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Butadiynyl-substituted η6-benzeneCr(CO)3 complexes 3 are very efficiently prepared by a copper catalyzed coupling of the phenylacetylene complex 1 and bromo alkynes 2. The transmission of electronic effects through the butadiynyl bridge operates by resonance mechanisms as established by correlations between Hammett's σp, σR and σ P+ parameters. Most interestingly, however, is an unusual thermal behavior that leads to intractable paramagnetic polymers of unknown structure. According to thermal analyses (thermal gravimetrical analysis, differential scanning calorimetry) the complexes 3 react in a thermal solid-state reaction under CO extrusion to give amorphous cross-linked polymers. © 2003 Elsevier B.V. All rights reserved.
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