Deprotonation, Deuteriation and Substitution of the Backbone of Some Azine Diphosphine Complexes of Palladium and Platinum: Crystal Structures of and
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Source and publish data:
Journal of the Chemical Society, Dalton Transactions p. 3311 - 3324 (1994)
Update date:2022-07-30
Topics:
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Authors:
Perera, Sarath D.
Shaw, Bernard L.
Thornton-Pett, Mark
Article abstract of DOI:10.1039/DT9940003311
Treatment of the azine diphosphine Z,Z-PPh2CH2CBut=N-N=CButCH2PPh2 I with (cod = cycloocta-1,5-diene) in CHCl3 in the presence of NEt3 gave the neutral deprotonated chloroplatinum (II) complex , containing an ene-hydrazone backbone.The corresponding bromo- and iodo-analogues were prepared from it by metathesis.The analogous chloropalladium(II) complex was prepared by treating I with in the presence of NEt3.Treatment of it with LiBr or MgMeI gave the corresponding bromo- and methyl-palladium(II) complexes, respectively.Treatment of the neutral complexes (M = Pt or Pd) with acids (HX) reprotonated the ene-hydrazone backbone to give the salts X 4 heptane-1-methanesulfonate, M = Pt or Pd>.Treatment of with 0.5 equivalent of NH2NH2*2HCl gave a mixture of the nine-membered ring complex and its isomeric chloride salt Cl.When , containing a nine-membered chelate ring, was heated to 75 deg C in C6H6 the methylplatinum(II) complex, , containing the terdentate dehydroazine ligand, was formed by oxidative addition of NH followed by reductive elimination of CH4.Treatment of the same PtMe2 complex with 1 equivalent of picric acid gave the picrate salt , which with 1,8-diazabicyclo<5.4.0>undec-7-ene (dbu) gave , and with MeI followed by NH4PF6 gave fac-PF6 which with dbu gave fac-.Treatment of with 1 equivalent of picric acid gave which with dbu gave .Treatment of I with (nb = norbornene) gave the bridged binuclear platinum(0) complex , containing an 18-atom ring.Treatment of this with MeO2CC<*>CCO2Me displaced the norbornene to form the corresponding bis(dimethyl acetylenedicarboxylate) complex.When the former was heated to 75 deg C in benzene was formed.The bis(norbornene)platinum(0) complex also underwent oxidative addition with MeI to give I, which with dbu gave .Methods of forming the di- and tetra-deuteriated complexes containing the azine backbone, and also mono- and tri-deuteriated complexes containing the dehydroazine backbone are discussed (M = Pt or Pd).A novel method of functionalising (e.g. alkylation and halogenation) the ligand backbone by electrophilic attack on the enamine carbon in complexes of type 4 is described.The crystal structures of and were determined.Proton, 31P and some 13C NMR data are given.
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Full text of DOI:10.1039/DT9940003311
