THE REACTIONS OF COMPLEXES WITH NUCLEOPHILES

Article abstract of DOI:10.1016/0022-328X(85)87280-6

The extent of the reaction of with CO in chloroform at ca. 20 deg C and 1 atmosphere pressure is markedly dependent on X.Thus when X = CL the reductive elimination of the tin(IV) halide, SnCl4, is complete within 30 minutes and is formed almost quantitatively but reversibly.When X = I no detectable reaction takes place, but when X = Br an intermediate situation is observed, with both reagent and product present in the reation mixture.On the other hand, te principal reactions of with both (PhO)3P and Ph3P (L) are CO substitutions to give .A limited amount of reductive elimination to give and may occur, but because it is reversible these side-products soon disappear.The course of the reactions of with CO depends on the P^III ligand L, and on X.Thus when L = (PhO)3P and X = Br the sole product is but when L = Ph3P and X = Br and then some are formed. does not appear to react with CO.When (X = Cl or Br) are dissolved in donor solvents such as tetrahydrofuran, acetone or acetonitrile, some reversible formation of takes place, but the sole isolable products have the empirical formulae .With pyridine (py) or 2,2'-bipyridyl (bipy), these last give blue and brown respectively.