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A series of cobalt(II) complexes of general formula [CoX 2 L 2 ] (X = Cl, Br, I, NO 3 , ClO 4 , NCS; L 2 = Ph 2 PCH 2 Si(CH 3 ) 2 CH 2 PPh 2 ) have been synthesised and characterised by electronic and infrared spectroscopy and by magnetic moment studies. The bidentate phosphine ligand is an analogue of 1,3-bis(diphenylphosphino)propane (dppp). X-ray analysis of the [CoBr 2 L 2 ] complex proves tetrahedral geometry at the metal centre with the bidentate phosphine exhibiting a bite angle of 101.54(6)°. A range of evidence supports the existence of tetrahedral geometry about the metal in all the complexes in both the solid state and solution. Electronic spectroscopy is diagnostic for the tetrahedral d 7 metal ion in each case, with the v 2 and v 3 transitions clearly visible. Calculations of D q and B ′, the RACAH parameter, have been performed for each complex; the relative magnitudes of B ′ indicate that the metal-phosphorus bonds are of increased covalency in comparison with Co(dppp) analogues. Magnetic moment studies show values of μ B in the range 4.4–4.9 B.M., as expected for tetrahedral cobalt(II). IR studies show that the nitrate and perchlorate ions in the respective complexes are bound in monodentate fashion, while the [Co(NCS) 2 (L 2 )] complex exhibits N-bonded thiocyanate groups. |
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