154991-88-5Relevant academic research and scientific papers
Deprotonation, Deuteriation and Substitution of the Backbone of Some Azine Diphosphine Complexes of Palladium and Platinum: Crystal Structures of and
Perera, Sarath D.,Shaw, Bernard L.,Thornton-Pett, Mark
, p. 3311 - 3324 (2007/10/02)
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-diazabicycloundec-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 MeO2CCCCO2Me 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.
Reactions of an Azine Diphosphine with Platinum(II) and Palladium(II) and the Formation of a Novel Heterocyclic Diphosphine Ligand. Crystal Structure of
Perera, Sarath D.,Shaw, Bernard L.,Thornton-Pett, Mark
, p. 3653 - 3660 (2007/10/02)
The azine diphosphine Z,Z-PPh2CH2C(But)=N-N=C(But)CH2PPh2 I was treated with (cod = cycloocta-1,5-diene) to give the dimethylplatinum(II) complex 1a containing a nine-membered chelate ring with an E,Z configuration for the bidentate azine diphosphine ligand.This complex undergoes oxidative addition with MeI to give the fac-trimethylplatinum(IV) complex 2.The corresponding platinium(II) complexes (X = CCC6H4Me-p 1b or Cl 1c) were also prepared.Treatment of trans- (R = Me or Ph) with I gave a hexanuclear species trans-t)=N-N=C(But)CH2PPh2>>6> 3a in which the azine diphosphine is acting as a bridging group and is still symmetrical, i.e. the configuration is still Z,Z.The palladium analogue 3b was made by treating or Na2 with I but might only be binuclear.This complex was unstable in hot chloroform and at 60 deg C (30 min) was completely converted into the salt 4a in which the azine diphosphine is tridentate with E,Z configuration and mutually trans-co-ordinated phosphorus donors and one of the azine nitrogens is co-ordinated.Treatment of with I and addition of NH4PF6 gave the platinum salt 4c; 4d was also prepared.On prolonged (8 d) heating in chloroform solution the bridged complex 3b was quantitatively converted into the novel and very stable heterocyclic complex 5a with loss of a molecule of benzene.Treatment of 5a with LiBr or NaI gave the corresponding dibromide 5b or diiodide 5c complexes.The crystal structure of 5c has been determined.The corresponding platinum complexes 5d-5f (X = Cl, Br or I) were also prepared and treatment of the dichloro complex with MgMeI gave the dimethyl complex 5g.Treatment of this dimethyl complex with an excess of MeI gave 6.Proton, 13C- and 31P- NMR and infrared data are given.
