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Issue 21, 2018
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Ni(II) complexes of the phosphine-oxime Ph2PC6H4-2-CH[double bond, length as m-dash]NOH

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Abstract

We report the solution and structural chemistry of nickel(II) complexes of the phosphine-oxime Ph2PC6H4-2-CH[double bond, length as m-dash]NOH (PCH[double bond, length as m-dash]NOH). PCH[double bond, length as m-dash]NOH invariably binds in a bidentate manner as illustrated by cis-Ni(PCH[double bond, length as m-dash]NOH)2Cl2 and cis-[Ni(PCH[double bond, length as m-dash]NOH)2]2+ (as its BF4 salt). Treatment of PCH[double bond, length as m-dash]NOH with Ni(OAc)2(H2O)4 gave charge-neutral trans-[Ni(PCH[double bond, length as m-dash]NO)2]0. Treatment of trans-[Ni(PCH[double bond, length as m-dash]NO)2]0 with BF3 gave [Ni(PCH[double bond, length as m-dash]NO)2BF2]BF4. The cation features a planar NiP2N2 center wherein the pair of oximate groups are linked by the difluoroboryl center. The 1 : 1 complexes of the oxime and the oximate are illustrated by [Ni(PCH[double bond, length as m-dash]NOH)Cl2]2 and [Ni(C6F5)(PCH[double bond, length as m-dash]NO)]2, which feature five- and four-coordinate Ni(II) centers, respectively. All complexes in this series hydrolyze to give the trinickel oxo-phosphine-oximate complex [Ni3(PCH[double bond, length as m-dash]NO)3O]+. One feature of the PCH[double bond, length as m-dash]NOH ligand is its wide bite angle combined with its protic OH center. These aspects are manifested in the structures of Ni(PCH[double bond, length as m-dash]NOH)2Cl2 and [Ni(PCH[double bond, length as m-dash]NOH)Cl2]2, which show intramolecular hydrogen bonding to terminal chloride ligands.

Graphical abstract: Ni(ii) complexes of the phosphine-oxime Ph2PC6H4-2-CH [[double bond, length as m-dash]] NOH

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Publication details

The article was received on 19 Apr 2018, accepted on 07 May 2018 and first published on 08 May 2018


Article type: Paper
DOI: 10.1039/C8DT01551A
Citation: Dalton Trans., 2018,47, 7256-7262
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    Ni(II) complexes of the phosphine-oxime Ph2PC6H4-2-CH[double bond, length as m-dash]NOH

    D. Basu, T. J. Woods and T. B. Rauchfuss, Dalton Trans., 2018, 47, 7256
    DOI: 10.1039/C8DT01551A

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