Phospholylsamarium(III) Complexes

Mono-phosphacyclopentadienyl bis(tetramethylaluminate) lanthanide complexes

“…for homoleptic [(g 5 -Dmp) 2 (l:g 1 ,g 5 -Dmp)Sm] 2 . 16 It is noteworthy that the additional phosphorus soft donor coordination (La1-P 3.1962(3) A ˚) does not affect the tetramethylaluminate bonding via a donor-induced AlMe 3 separation. 14 Formally each lanthanum centre is 8-coordinated adopting a pseudo-octahedral coordination geometry with the Tmp ligand and a bridging methyl group in the apical positions (Ct-La1-C6, 174.75 • ).…”

Heterocyclopentadienyl Complexes of Group-3 Metals

“…The chemistry of (phospholyl)uranium complexes is therefore not only influenced by steric but also by electronic factors. [22] Finally, further evidence for the accessibility of the phosphorus lone pairs was found by the X-ray characterisation of two UϪNi heterobimetallic compounds: [Cl 2 U(µ:η 5 ,η 1 -Tmp) 2 Ni] (20) and [{Cl 2 U(µ:η 5 ,η 1 -Tmp) 2 (µ-Tmp)Ni} 2 ] [28] (21).…”

“…An ate complex of polymeric two-dimensional structure, which retains KCl, was obtained instead. Its Xray structure has been determined and is that of [{(η 5 -Tmp)Sm(µ:η 5 ,η 1 -Tmp) 2 (µ-Cl)K(η 6 -toluene)} n ] [20] (10).…”

“…Under the same conditions with the Dmp ligand, a neutral tris(Dmp) dimer, [{(η 5 -Dmp) 2 (µ:η 5 ,η 1 -Dmp)Sm} 2 ] (11), was obtained [20] . In this case, since the Dmp ligand is smaller, the Sm atom can achieve a c.n.…”

f‐Block Phospholyl and Arsolyl Chemistry

“…These diamagnetic Ln III complexes were characterised by multinuclear NMR spectroscopy, with each showing one signal in their 31 P NMR spectra ( δ P : 84.0 ppm, 1 J YP =6.4 Hz for Ln=Y; δ P : 78.6 ppm for Ln=Lu), with 89 Y NMR data used to corroborate the coupling in the former complex and assign η 5 ‐bound Tmp ligands, but no solid‐state structures were obtained. In 1995, Nief and co‐workers reported the synthesis of the Sm III phospholyl complexes [{Sm(η 5 ‐Tmp)(μ:η 5 ,η 1 ‐Tmp) 2 (μ‐Cl)K(C 7 H 8 )} 2 ] ∞ ( 32 ) and [{Sm(η 5 ‐Mhp) 2 (μ:η 5 ,η 1 ‐Mhp)} 2 ] ( 33 ; Figure 11) by the reactions of SmCl 3 with three equivalents of the respective group 1 ligand transfer agents K(Tmp) and K(Mhp) in toluene at reflux [34] . The solid‐state structure of salt‐occluded 32 revealed two crystallographically distinct Sm III centres, each with one terminal η 5 ‐Tmp (Sm−P: 2.953(3) Å), a μ:η 5 ,η 1 ‐Tmp that is η 5 ‐bound to Sm (Sm−P: 2.924(4) Å) and a μ:η 5 ,η 1 ‐Tmp that is η 1 ‐bound to Sm (Sm−P: 2.931(4) Å); a chloride completes the Sm coordination spheres that also bridge to K, which are in turn η 6 ‐bound by toluene and η 5 ‐bound by bridging phospholyls to give a net‐like structure.…”