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

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

Abstrakt

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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Informacje szczegółowe

Kategoria:
Publikacja w czasopiśmie
Typ:
artykuł w czasopiśmie wyróżnionym w JCR
Opublikowano w:
DALTON TRANSACTIONS nr 47, wydanie 30, strony 10213 - 10222,
ISSN: 1477-9226
Język:
angielski
Rok wydania:
2018
Opis bibliograficzny:
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:
Cyfrowy identyfikator dokumentu elektronicznego (otwiera się w nowej karcie) 10.1039/c8dt01977k
Weryfikacja:
Politechnika Gdańska

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