| Popis: |
Reaction of 1,2-diisocyanobenzene with [Fe 2 Cp 2 (CO) 3 NCMe] (Cp=η-cyclopentadienyl) (1:2) yields the tetranuclear complex [{Fe 2 CP 2 (CO) 2 (μ-CO)} 2 (μ 4 -CNC 6 H 4 NC)] ( 2 ) which in solution appears to exist as a mixture of cis and trans isomeric forms. 2 may be diprotonated to yield [{Fe 2 Cp 2 (CO) 3 } 2 (μ 4 -CN(H)C 6 H 4 N(H)C)](BF 4 ) 2 ( 3 ), monoalkylated to give [{Fe 2 Cp 2 (CO) 3 } 2 (μ 4 -CN(R)C 6 H 4 NC)]BF 4 (R=Me ( 4 ), Et (5)) and oxidatively cleaved with one molecule of I 2 to give [FeCp(I)(CO) 2 ] and the asymmetric species [{Fe 2 Cp 2 (CO) 3 }CNC 6 H 4 NC{FeCp(I)CO}] ( 6 ). In addition, 2 acts as a bidentate ligand towards the Lewis acidic metal halides FeCl 2 , PdCl 2 , ZnCl 2 , ZnI 2 and CdI 2 giving rise to surprisingly stable pentanuclear supercomplexes ( 7a–e ) which have been characterized by elemental analyses and IR and NMR ( 1 H, 13 C) spectra. Of 7c, an X-ray structure analysis has been carried out which for the first time assesses the μ 3 -(C,C,N) bridging mode of isocyanide in a non-cluster molecule. The most striking stereochemical features are the various gross distortions and deviations from more idealized geometries which are undoubtedly governed by the steric overcrowding in the molecule. |
