The influence of transannular interactions on the redox properties of the tricarbonylchromium complexes of ortho-, meta- and para-[2.2]cyclophane

lThe redox behaviour of the [2.2]cyclophane complexes, [Cr(CO)(3)(eta(6)-C16H16)][ortho (1,2), meta (1,3) and para (1,4) isomers], has been examined by cyclic voltammetry in 0.2 mor dm(-3) [NBu4][PF6]-CH2Cl2. The complexes display a one-electron oxidation in the region +0.7-+1.0 V (vs. Ag-AgCl), with the reversible half-wave potential varying in the order ortho > meta > pain. The variation in reversible potential for the oxidation profess indicates that the three cyclophane isomers impart different degrees of stabilisation on the {Cr(CO)(3)} moiety, in accord with the anticipated variation in the inter-ring pi-pi interaction within ortho-, meta- and para-cyclophane. The IR spectra of the [Cr(CO)(3)(eta(6)-C16H16)](+.) radical cations have been collected by in situ spectroelectrochemical electrogeneration. Despite the different reversible potentials for the oxidation of the three [Cr(CO)(3)(eta(6)-C16H16)](z) complexes, their IR spectra, both in the neutral and cationic states, are all quite similar, with the A(1) and E bands occurring in the region 1961-1956 and 1887-1876 cm(-1) (z = 0) and 2071-2068 and 2006-2003 cm(-1) (z = 1 +) respectively. The stability of the one-electron oxidised products, as judged by cyclic voltammetry, IR and EPR spectroelectrochemistry, also varies with cyclophane isomer, in the order para > meta > ortho. The stability of the [Cr(CO)(3)(eta(6)-C16H16-1,4)](+.) cation is such that it has also been characterised by EPR spectroscopy. The EPR spectrum consists of a rhombic pattern of three lines at g = 2.0860, 2.0374 and 1.9940 G corresponding to g(1), g(2) and g(3).