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Reactions of an Azine Diphosphine with Platinum(II) and Palladium(II) and the Formation of a Novel Heterocyclic Diphosphine Ligand. Crystal Structure of

DOI: 10.1039/DT9930003653

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 3653 - 3660 (1993)

Update date:2022-08-02

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Authors:

Perera, Sarath D.Perera, Sarath D.

Shaw, Bernard L.Shaw, Bernard L.

Thornton-Pett, MarkThornton-Pett, Mark

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Article abstract of DOI:10.1039/DT9930003653

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-<1H> and 31P-<1H> NMR and infrared data are given.

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Product name:{PtCl(C6H5)2PCH2C(C(CH3)3)N2C(C(CH3)3)CH2P(C6H5)2}(1+)*PF6(1-)={PtCl(C6H5)2PCH2C(C(CH3)3)N2C(C(CH3)3)CH2P(C6H5)2}PF6

Cas No:154991-83-0

154991-83-0

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