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.
Authors
Additional information
- DOI
- Digital Object Identifier link open in new tab 10.1039/c8dt01977k
- Category
- Publikacja w czasopiśmie
- Type
- artykuł w czasopiśmie wyróżnionym w JCR
- Language
- angielski
- Publication year
- 2018
