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Issue 18, 2011
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Mononuclear and dinuclear palladium and nickel complexes of phosphinimine-based tridentate ligands

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Abstract

The tridentate bis-phosphinimine ligands O(1,2-C6H4N[double bond, length as m-dash]PPh3)21, HN(1,2-C2H4N[double bond, length as m-dash]PR3)2 (R = Ph 2, iPr 3), MeN(1,2-C2H4N[double bond, length as m-dash]PPh3)24 and HN(1,2-C6H4N[double bond, length as m-dash]PPh3)25 were prepared. Employing these ligands, monometallic Pd and Ni complexes O(1,2-C6H4N[double bond, length as m-dash]PPh3)2PdCl26, RN(1,2-CH2CH2N[double bond, length as m-dash]PPh3)2PdCl][Cl] (R = H 7, Me 8), [HN(1,2-CH2CH2N[double bond, length as m-dash]PiPr3)2PdCl][Cl] 9, [MeN(1,2-CH2CH2N[double bond, length as m-dash]PPh3)2PdCl][PF6] 10, [HN(1,2-CH2CH2N[double bond, length as m-dash]PPh3)2NiCl2] 11, [HN(1,2-CH2CH2N[double bond, length as m-dash]PR3)2NiCl][X] (X = Cl, R = iPr 12, X = PF6, R = Ph 13, iPr 14), and [HN(1,2-C6H4N[double bond, length as m-dash]PPh3)2Ni(MeCN)2][BF4]Cl 15 were prepared and characterized. While the ether-bis-phosphinimine ligand 1 acts in a bidentate fashion to Pd, the amine-bis-phosphinimine ligands 2–5 act in a tridentate fashion, yielding monometallic complexes of varying geometries. In contrast, initial reaction of the amine-bis-phosphinimine ligands with base followed by treatment with NiCl2(DME), afforded the amide-bridged bimetallic complexes N(1,2-CH2CH2N[double bond, length as m-dash]PR3)2Ni2Cl3 (R = Ph 16, iPr 17) and N(1,2-C6H4N[double bond, length as m-dash]PPh3)2Ni2Cl318. The precise nature of a number of these complexes were crystallographically characterized.

Graphical abstract: Mononuclear and dinuclear palladium and nickel complexes of phosphinimine-based tridentate ligands

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Publication details

The article was received on 22 Jan 2011, accepted on 22 Feb 2011 and first published on 22 Mar 2011


Article type: Paper
DOI: 10.1039/C1DT10131E
Citation: Dalton Trans., 2011,40, 4918-4925
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    Mononuclear and dinuclear palladium and nickel complexes of phosphinimine-based tridentate ligands

    R. Cariou, F. Dahcheh, T. W. Graham and D. W. Stephan, Dalton Trans., 2011, 40, 4918
    DOI: 10.1039/C1DT10131E

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