Abstract
Interest in fluorophosphines as ligands was initiated when Chatt1,2 established the formula Pt(PF3)2X2 for a compound described years ago by Schutzenberger and Fontaine3 and later by Moisson.4 As expected, Pt(PF3)2X2 has square planar cis geometry. The ability of the PF3 unit to serve as a coordination ligand put severe strains on existing coordination theory, since electronegative fluorines attached to the phosphorus would be expected to pull back the phosphorus electron pair and seriously reduce its dδ-bonding ability. Chatt rationalized the existence of Pt(PF3)2X2 by suggesting that d electrons from the platinum were donated back to the d orbitals of the phosphorus to give dπ-dπ;-bonding. The electronegative fluorines attached to the phosphorus would build up the effective positive charge on the central phosphorus atom, and lower the energy of the 3d orbitals enough to permit their use in bonding.
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References
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Parry, R.W. (1969). Coordination Compounds Containing Fluorophosphine Ligands. In: Kirschner, S. (eds) Coordination Chemistry. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-6555-4_13
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DOI: https://doi.org/10.1007/978-1-4899-6555-4_13
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