Stable ‐ESiMe3 Complexes of CuI and AgI (E=S,Se) with NHCs: Synthons in Ternary Nanocluster Assembly

As a part of efforts to prepare new “metallachalcogenolate” precursors and develop their chemistry for the formation of ternary mixed‐metal chalcogenide nanoclusters, two sets of thermally stable, N‐heterocyclic carbene metal–chalcogenolate complexes of the general formula [(IPr)Ag?ESiMe₃] (IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene; E=S, 1 ; Se, 2 ) and [(iPr₂‐bimy)Cu?ESiMe₃]₂ (iPr₂‐bimy=1,3‐diisopropylbenzimidazolin‐2‐ylidene; E=S, 4 ; Se, 5 ) are reported. These are prepared from the reaction between the corresponding carbene metal acetate, [(IPr)AgOAc] and [(iPr‐bimy)CuOAc] respectively, and E(SiMe₃)₂ at low temperature. The reaction of [(IPr)Ag?ESiMe₃] 1 with mercury(II) acetate affords the heterometallic complex [{(IPr)AgS}₂Hg] 3 containing two (IPr)Ag?S^? fragments bonded to a central Hg^II, representing a mixed mercury–silver sulfide complex. The reaction of [(iPr₂‐bimy)Cu‐SSiMe₃]₂, which contains a smaller N‐heterocyclic‐carbene, with mercuric(II) acetate affords the high nuclearity cluster, [(iPr₂‐bimy)₆Cu₁₀S₈Hg₃] 6 . The new N‐heterocyclic carbene metal–chalcogenolate complexes 1 , 2 , 4 , 5 and the ternary mixed‐metal chalcogenolate complex 3 and cluster 6 have been characterized by multinuclear NMR spectroscopy (¹H and ¹³C), elemental analysis and single‐crystal X‐ray diffraction.     

Spin-reorientations in DyFe10Cr2: A57Fe Mössbauer study

We have used⁵⁷Fe Mössbauer spectroscopy carried out on a magnetically aligned powder sample of DyFe₁₀Cr₂ to investigate its magnetic structure at low temperatures. Previous susceptibility measurements by Stefanski [1] demonstrated the occurrence of a spin-reorientation in DyFe₁₀Cr₂ at 190 K. Subsequent work by Yang et al. [2] confirmed this reorientation, at 175 K, and also demonstrated a second spin-reorientation at 75 K. By invoking the example of the RFe₁₁Ti series of compounds, Yang et al. claimed that the reorientation at 175 K is axis-cone type and the 75 K reorientation is cone-plane type. Our measurements confirm the nature of these reorientations.     

Novel ternary iron-rich,rare-earth iron silicides: R3(Fe1−x Si x )22 (x ∼ 0.16)

In our search for new ternary rare-earth (R) iron silicon intermetallic compounds, a novel ternary phase with the chemical formula R₃Fe_18.5Si_3.5 has been identified with the RFeSi ratio in the range of 12–1574–7810–12. We have studied compounds with R=Gd, Tb, Dy, Ho, Er, Tm and Lu. All of the samples, except for R=Lu, form the new ternary phase3–22. X-ray diffraction data suggest that for R=Gd and Tb, the crystal structure is the rhombohedral Th₂Zn₁₇-type structure and for R=Dy, Ho, Er and Tm, the hexagonal Th₂Ni₁₇-type structure. We suggest that a 1/4 replacement of the R sites by Fe(Si) dumbbells in the CaCu₅-type structure leads to the new3–22 phase, which is an ordered version of the TbCu₇-type structure.⁵⁷Fe Mössbauer spectroscopy has been used to determine the hyperfine parameters of the⁵⁷Fe nuclei in the3–22 compounds. At 295 K, the average hyperfine field of the new3–22 phase ranges from 19.8 T (R=Ho) to 22.2 T (R=Gd). Thermogravimetric analysis (TGA) of these compounds gives Curie temperatures in the range 467 K (Tm)–549 K (Gd). Furthermore, our Mössbauer analysis enables us to investigate the preferential site occupancy shown by Si in these structures.