A series of 3,4-dicarboethoxy-N-pyrrolyl phosphine
ligands
(R2P−NC4H2(CO2Et)2)
is
described. A number of techniques, including reaction calorimetry,
infrared spectroscopy,
and X-ray crystallography, demonstrate that these ligands are potent
π-acceptors and that
the electronic substituent parameter χi for the
3,4-(EtO2C)2C4H2N
moiety is ca. 16, placing
it in a position between fluorine and chlorine.
The fluoroaryl phosphines P{C6H3(CF3)2-3,5}3 (La) and P(C6F5)3 (Lb) form the complexes trans-[MCl2(La)2] and trans-[MCl2(Lb)2](M = Pd or Pt) which have been isolated and fully characterised. 31P NMR studies of competition experiments show that the stability of trans-[PdCl2L2] is in the order L = Lb< La
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