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The new diphosphanylphosphido complexes of tungsten(VI) and molybdenum(VI). Their synthesis, structures and properties
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.
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- Category:
- Articles
- Type:
- artykuł w czasopiśmie wyróżnionym w JCR
- Published in:
-
DALTON TRANSACTIONS
no. 47,
edition 30,
pages 10213 - 10222,
ISSN: 1477-9226 - Language:
- English
- Publication year:
- 2018
- Bibliographic description:
- Wiśniewska A., Grubba R., Ponikiewski Ł., Zauliczny M., Pikies J.: The new diphosphanylphosphido complexes of tungsten(VI) and molybdenum(VI). Their synthesis, structures and properties// DALTON TRANSACTIONS. -Vol. 47, iss. 30 (2018), s.10213-10222
- DOI:
- Digital Object Identifier (open in new tab) 10.1039/c8dt01977k
- Verified by:
- Gdańsk University of Technology
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