Abstract
E.s.r. and u.v.–visible spectral studies of the complexes [CoX2(PPhF2)3](X = Br or I) indicate a distorted trigonalbipyramidal co-ordination geometry at cobalt with two axial and one equatorial phosphorus ligand. Cobalt-59 hyperfine and 31P superhyperfine coupling constants have been obtained by analysis of the e.s.r. spectra of frozen solutions in dichloromethane–paraffin oil at 100 K and interpreted in terms of delocalisation of unpaired electron spin density. The X-ray structure of [CoBr2(PPhF2)3] has been determined in order to substantiate the results of the spectroscopic investigations. Crystals of [CoBr2(PPhF2)3] are monoclinic, P21/n, with a= 8.428(4), b= 16.304(8), c= 17.206(9)A, β= 98.58(6)°, Z= 4. The molecules display a trigonal-bipyramidal geometry with the two bromine atoms equatorially substituted. Principal bond lengths are: Co–Pax. 2.158(5) and 2.158(5), Co–Peq. 2.120(5), and Co–Breq. 2.383(2) and 2.367(3)A.
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