Rare‐Earth Metal Phenyl(trimethylsilyl)amide Complexes

Abstract

The reactions of common rare-earth metal chloride, borohydride, and triflate precursors -LnCl 3 (thf) x , Ln(BH 4 ) 3 (thf) 3

Syntheses of lanthanide monochloride and monoborohydride complexes supported by bridged bis(guanidinate) ligand and the use of borohydride complexes in polymerization of cyclic esters

“…The BH 4 À group is h 3 -bonded to the Ln atom via three hydrogen atoms. The NdeB distance of 2.678(7) Å in 6 is in the range of the previously reported NdeB distances of related complexes [27,43] and the distance of YbeB, 2.626(4) Å in 7 is shorter than 2.800 Å in (MeOCH 2 CH 2 C 5 H 4 ) 2 YbBH 4 with a h 2 -BH 4 À group [43]. The YeB distance of 2.644(7) Å in 8 compares to the value in 7, but is longer than those found in Y complexes with a h 3 -…”

“…Removing the DME solvent, washing the residues with hexane, and crystallization from a mixture of THF and hexane at 0 C gave the product 5 as yellow crystals (1.1 g, 82%). C 27 …”

“…Compound 7 was isolated as yellow crystals (0.83 g, 65%). C 27 3.9. Synthesis of LYBH 4 (DME) (8) This complex was prepared following the procedure described above for 6 starting from NaBH 4 (2.5 mmol, 0.095 g) in THF (20 mL) and 4 (2.0 g, 2.5 mmol) in THF (20 mL …”

Homoleptic Trigonal Planar Lanthanide Complexes Stabilized by Superbulky Silylamide Ligands

“…9 [Ln(N″) 3 ] complexes are standard reagents and starting materials in Ln synthetic chemistry, 13 and the use of N″ as a stabilizing ancillary ligand has been demonstrated in Ln(III) dinitrogen complexes obtained from reduction mixtures such as [{Ln(N″) 2 (THF)} 2 -(μ-η 2 :η 2 -N 2 )] (Ln = Y, Nd, Gd, Tb, Dy, Ho, Er, Tm, Lu) 18 and [K(18-crown-6)(THF) n ][{Ln(N″) 2 (THF)} 2 (μ-η 2 :η 2 -N 2 )] (Ln = Gd, Dy, n = 0; Ln = Tb, Ho, Er; n = 2). 19 With 22 We reasoned that very bulky bis-silylamides could be utilized to prepare homoleptic f-element complexes with unusual geometries and enhanced stability. Noting that the synthesis of [{K[μ-N(SiMe 2 Bu t )(SiMe 3 )]} 2 ] ∞ 23 could be achieved from simple and commercially available starting materials, 24 we modified these procedures to prepare more sterically demanding bis-silylamides.…”

Assembling High-Temperature Single-Molecule Magnets with Low-Coordinate Bis(amido) Dysprosium Unit [DyN 2 ] + via Cl–K–Cl Linkage

“…Complexes 1-3 were synthesized using the reactions between anhydrous DyCl 3 and potassium phenyl(trimethylsilyl)amide K[N RR' ] 54 in tetrahydrofuran (THF) at room temperature, followed by crystallization in toluene, hexane, and THF, respectively. Complex 4 was obtained by the crystallization of 1 in hexane (Scheme 1).…”