Inorganic Chemistry, Vol.41, No.2, 416-420, 2002
High-vacuum pyrolysis of Zr(2,3,7,8,12,13,17,18-octaethylporphyrin)(PhC equivalent to CPh) as a route to nover Zr species: X-ray structure of a hetero-triply bridged species, [(OEP-Zr(mu-Cl)]2(mu-O)
The Zr-II porphyrin derivative, Zr(OEP)(PhCequivalent toCPh), OEP = 2,3,7,8,12,13,17,18-octaethylporphyrin, rapidly loses diphenylacetylene upon heating at 150 degreesC and 2 muTorr generating a highly reactive paramagnetic species. Its reaction with CH2Cl2 yields a bimetallic derivative assigned as [Zr(OEP)(mu-Cl)](2)(mu-CH2), which hydrolyzes rapidly to [Zr(OEP)(mu-Cl)](2)(mu-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 18degrees tilt between the two porphyrin rings.