2024/09/16 by Jack E. Baldwin, Adam Brookfield, George F. S. Whitehead +4 · 1 voice
Chemistry · #Organometallic Complex Synthesis and Catalysis #Synthesis and characterization of novel inorganic/organometallic compounds #Coordination Chemistry and Organometallics
paper · pdf · doi:10.1021/acs.inorgchem.4c02888
openalex publication_date 2024/09/16 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/01
High Resolution Image Download MS PowerPoint Slide While lanthanide (Ln) silylamide chemistry is mature, the corresponding silylphosphide chemistry is underdeveloped, with [SmP(SiMe 3 ) 2 μ-P(SiMe 3 ) 2 3 Sm(THF) 3 ] being the sole example of a structurally authenticated Ln(II) silylphosphide complex. Here, we expand the Ln(II) P(SiMe 3 ) 2 chemistry through the synthesis and characterization of nine complexes. The dinuclear “ate” salt-occluded complexes [Ln[P(SiMe 3 ) 2 ] 3 (THF) 2 (μ-I)K 3 (THF)] ( 1-Ln; Ln = Sm, Eu) and polymeric “ate” complex [KYbP(SiMe 3 ) 2 3 μ-K[P(SiMe 3 ) 2 ] 2 ] ∞ ( 2-Yb ) were prepared by the respective salt metathesis reactions of parent [LnI 2 (THF) 2 ] (Ln = Sm, Eu, Yb) with 2 or 3 equiv of KP(SiMe 3 ) 2 in diethyl ether. The separate treatment of these complexes with either pyridine or 18-crown-6 led to the formation of the mononuclear solvated adducts trans -[LnP(SiMe 3 ) 2 2 (py) 4 ] ( 3-Ln; Ln = Sm, Eu, Yb) and [LnP(SiMe 3 ) 2 2 (18-crown-6)] ( 4-Ln; Ln = Sm, Eu, Yb), with concomitant loss of KP(SiMe 3 ) 2 . The complexes were characterized by a combination of NMR, electron paramagnetic resonance (EPR), attenuated total reflectance infrared (ATR-IR), electronic absorption and emission spectroscopies, elemental analysis, SQUID magnetometry, and single crystal X-ray diffraction. We find that these complexes contrast with those of related Ln(II) bis(silyl)amide complexes due to differences in ligand donor atom hardness and ligand steric requirements from Ln−P bonds being longer than Ln−N bonds. This leads to higher coordination numbers, shorter luminescence lifetimes, and smaller eas y -axis magnetic anisotropy parameters.