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Issue 5, 2001
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First observation of metal-mediated nitrileimine coupling giving ligated 1,3-diaza-1,3-dienes

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Abstract

Coupling between benzophenone imine and coordinated organonitriles in the platinum(IV) complexes [PtCl4(RCN)2] (R = Me or Et) proceeded rapidly under mild conditions to afford the 1,3-diaza-1,3-diene compounds [PtCl4{NH[double bond, length half m-dash]C(R)N[double bond, length half m-dash]CPh2}2] in good yield and this reaction is the first observation of metal-assisted nucleophilic addition of an imine to a ligated nitrile. [PtCl4{NH[double bond, length half m-dash]C(R)N[double bond, length half m-dash]CPh2}2] were reduced to the corresponding platinum(II) complexes [PtCl2{NH[double bond, length half m-dash]C(R)N[double bond, length half m-dash]CPh2}2] by the carbonyl-stabilized phosphorus ylide Ph3P[double bond, length half m-dash]CHCO2Me. The [PtCl2{NH[double bond, length half m-dash]C(Me)N[double bond, length half m-dash]CPh2}2] complex was also detected in a mixture formed in the reaction between the platinum(II) nitrile complex [PtCl2(MeCN)2] and Ph2C[double bond, length half m-dash]NH, but the selectivity of the platinum(II)-mediated nitrileimine coupling was enhanced by employing for the reaction with benzophenone imine the phenyl cyanide complex [PtCl2(PhCN)2] to give [PtCl2(NH[double bond, length half m-dash]CPh2){NH[double bond, length half m-dash]C(Ph)N[double bond, length half m-dash]CPh2}]. Liberation of 1,3-diaza-1,3-dienes was exemplified by the reaction of [PtCl2{NH[double bond, length half m-dash]C(Et)N[double bond, length half m-dash]CPh2}2] with two equivalents of 1,2-bis(diphenylphosphino)ethane in CHCl3 to give, along with free NH[double bond, length half m-dash]C(Et)N[double bond, length half m-dash]CPh2 retained in solution, the solid complex [Pt(dppe)2]Cl2. All isolated metal complexes were characterized by elemental analyses, FAB mass spectrometry, IR, 1H, 13C-{1H} and 195Pt NMR spectroscopies and cis-[PtCl4{Z-NH[double bond, length half m-dash]C(Et)N[double bond, length half m-dash]CPh2}2] also by X-ray single-crystal diffraction.

Graphical abstract: First observation of metal-mediated nitrile–imine coupling giving ligated 1,3-diaza-1,3-dienes

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Publication details

The article was received on 10 Oct 2000, accepted on 20 Dec 2000 and first published on 16 Feb 2001


Article type: Paper
DOI: 10.1039/B008154J
J. Chem. Soc., Dalton Trans., 2001, 560-566

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    First observation of metal-mediated nitrileimine coupling giving ligated 1,3-diaza-1,3-dienes

    D. A. Garnovskii, V. Yu. Kukushkin, M. Haukka, G. Wagner and A. J. L. Pombeiro, J. Chem. Soc., Dalton Trans., 2001, 560
    DOI: 10.1039/B008154J

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