LIGAND-SUBSTITUTION REACTIONS OF NEUTRAL AND CATIONIC ALLYL(CYCLO-OCTA-3,5-DIENE)PLATINUM COMPLEXES

DOI: 10.1039/DT9800001208

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1208 - 1219 (1980)

Update date:2022-07-29

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Authors:

Boag, Neil M.

Green, Michael

Spencer, John L.

Stone, F. Gordon A.

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Article abstract of DOI:10.1039/DT9800001208

Treatment of the compound (X=Cl or Br; cod=cyclo-octa-1,5-diene) with pyridine (py) affords 3-C3H5)(py)>.In solution these complexes dimerise to form allyl-bridged binuclear species.Reaction of the complex > with allyl halides, or reaction of (X=Cl, allyl=C3H5 or C3H4Ph-3; X=Br, allyl=C₃H₅ or C3H4Me-3) with 1 mol of P(C6H11)3 affords the compounds 3-allyl).Addition of 2 mol of PPh3 or P(C6H11)3, or 1 equivalent of Ph2PCH2CH2PPh2 (dppe), affords complexes of the type .Treatment of the salts 3-allyl)(cod)> (allyl=C3H5 or C3H4Me-3) with py, PPh3, or dppe gives 3-allyl)(L2)<>BF4> (L2=2py, 2PPh3, or dppe).In contrast, 1 mol of PPh3 followed by 1 equivalent of CO, Bu^tNC, or py yields the complexes 3-C3H5)(PPh3)L> (L = CO, CNBu^t, or py) possibly via the intermediacy of 3-C3H5)(PPh3)>.Excess of Bu^tNC or py affords the ?-allylic species .In a similar manner, the tris(trimethyl phosphite) complexes 3> (allyl=C3H5, C3H4Me-3, or C3H4Ph-3) have been synthesized.Detailed n.m.r. studies (¹H, ¹³C, ³¹P, variable-temperature) of these complexes has led to an understanding of their behaviour in solution.

Full text of DOI:10.1039/DT9800001208

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