Abstract
Octacarbonyldicobalt reacts with the tritertiary phosphine 1,1,1-tris(diphenylphosphinomethyl)ethane (TDPME) to give the ionic complex [Co(CO)2TDPME][Co(CO)4]. Treatment of [Co(CO)2TDPME][Co(CO)4] with Na[B(C6H5)4], HClO4 and CH3J yields the cobalt(I)-salts [Co(CO)2TDPME]X [X == B(C6H5)4, ClO4, J]. With CH3J, [Co(CO)2TDPME]J can also be converted to Co(CO)2(J)(R2PCH2)2C(CH3)[CH2PR2CH3 +]J-in which TDPME is acting as a bidentate ligand. [Co(CO)2TDPME]ClO4 forms with KCN the non ionic compound Co(CN)(CO)(TPDME). The IR spectra of all compounds between 2100 and 400 cm-1 are reported. Based on Raman polarization data a tetragonal pyramid has been proposed for the five-coordinated cobalt(I) in the cation [Co(CO)2TDPME]+.

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