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The new diphosphanylphosphido complexes of tungsten(VI) and molybdenum(VI). Their synthesis, structures and properties

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Abstract

We report on the reactivity of R2P–P(Li)–PR′2 (R = tBu, iPr, R′ = NEt2, iPr) towards diimido complexes [(dippN)2MCl2·dme] (M = Mo, W and dipp = 2,6-iPr2C6H3). A series of new complexes with diphosphanylphosphido ligands R2P–P–PR′2 were isolated. The solid-state structures of [(dippN)2M(Cl)(1,2-η-iPr2P–P–PiPr2)] (2Mo and 2W) and [(dippN)2M(Cl){1,2-η-tBu2P–P–P(NEt2)2}] (3Mo and 3W) were established by single-crystal X-ray diffraction analysis and indicate a side-on geometry of the R2P–P–PR′2 moiety. 3W and 3Mo are the first triphosphorus complexes with the amido ligand NEt2 on the P atom. [(dippN)2M(Cl)(1,2-η-tBu2P–P–PtBu2)] (1Mo and 1W) and 3Mo and 3W display similar side-on geometry in solution and in the solid state. By contrast, 2Mo and 2W reveal a dynamic behavior in solution. For the first time, the reactivity of diphosphanylphosphido complexes towards different nucleophiles was studied. The complexes react with the phosphorus nucleophile Ph2PLi, yielding phosphanylphosphinidene complexes [(dippN)2M(Cl)(η2-P-PR2)] Li+ (M = Mo, W) together with related diphosphanes R′2P–PPh2. Carbon nucleophile MeLi does not yield [(dippN)2M(Cl)(η2-P-PR2)] Li+ but substitutes a Cl ligand at the metal center. Moreover, we compare the coordination of the R2P–P–PR′2 moiety to different metal centers based on DFT methods.

Graphical abstract: The new diphosphanylphosphido complexes of tungsten(vi) and molybdenum(vi). Their synthesis, structures and properties

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Publication details

The article was received on 16 May 2018, accepted on 04 Jul 2018 and first published on 05 Jul 2018


Article type: Paper
DOI: 10.1039/C8DT01977K
Citation: Dalton Trans., 2018, Advance Article
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    The new diphosphanylphosphido complexes of tungsten(VI) and molybdenum(VI). Their synthesis, structures and properties

    A. Wiśniewska, R. Grubba, Ł. Ponikiewski, M. Zauliczny and J. Pikies, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C8DT01977K

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