High-vacuum pyrolysis of Zr(2,3,7,8,12,13,17,18-octaethylporphyrin)(PhC triple bond CPh) as a route to novel Zr species: X-ray structure of a hetero-triply bridged species, [(OEP)Zr(mu-Cl)](2)(mu-O).

Abstract

The ZrII porphyrin derivative, Zr(OEP)(PhC⋮CPh), OEP = 2,3,7,8,12,13,17,18-octaethylporphyrin, rapidly loses diphenylacetylene upon heating at 150 °C and 2 μTorr generating a highly reactive paramagnetic species. Its reaction with CH2Cl2 yields a bimetallic derivative assigned as [Zr(OEP)(μ-Cl)]2(μ-CH2), which hydrolyzes rapidly to [Zr(OEP)(μ-Cl)]2(μ-O). The latter complex is the first crystallographically characterized halogen-bridged metalloporphyrin dimer. As such, it possesses a number of interesting structural features, including an 18° tilt between the two porphyrin rings.