Synthesis, multinuclear magnetic resonance spectra, and chemistry of some complexes [(μ-SR)₆(MX)₄]²⁻ (R = alkyl; M = Zn or Cd; X = Cl, Br, or I) and the X-ray structural analysis of (Et₄N)₂[(μ-SPrⁱ)₆(CdBr)₄]

Abstract

. 70,779 (1992). The self-assembly method has been used to prepare a wide range of new adamantane-like anions of the type [(k-SR) (1), and Z = 4. The structure was refined to R(R,,.) = 0.0663(0.0703) with the use of 2669 unique data with I > 2.5u(I). The anion contains an adamantane-type (k,-S),Cd, cage composed of a nearly regular Cd4 tetrahedron and a distorted S6 octahedron, the irregularity of which is caused by 1,3-interactions of the substituent groups on the sulfur atoms. The axial or equatorial dispositions of the six alkyl groups in the four fused M3S3 rings are [aae, aae, aee, aee]. For the zinc-group elements, this is the first example of an adamantane-like (p-Salkyl),M, cage that has been characterized crystallographically.Key words: cadmium complex, cadmium-1 1111 13 NMR, thiolate complex, X-ray analysis, zinc complex.

Sulfur K-edge extended X-ray absorption fine structure spectroscopy of homoleptic thiolato complexes with Zn(II) and Cd(II)

“…[(l-SR) 6 (MX) 4 ] type complexes were reported from a structural viewpoint. The terminal positions on the adamantane-like cage can be substituted by other ligands such as sulfide [S 4 M 10 (SPh) 16 ] 2À (M = Zn(II) and Cd(II)) [42,43], halogenide ions [(l-SPh) 6 (ZnX) 4 ] 2À (X = Cl, Br, and I) [44], [(l-SPh) 6 (ZnSPh) 2 (ZnCl) 2 ] 2À [45], [(l-S-iPr) 6 (CdBr) 4 ] 2À [46], [(l-EPh) 6 (CdBr) 4 ] 2À (E = S and Se) [47], and phosphine [(l-S-iPr) 6 (CdPPh 3 ) 2 (CdOClO 3 ) 2 ] [48]. The complex substituted by solvent, [(l-SPh) 6 Zn 4 -(SPh)(CH 3 OH)] À [49], was also structurally characterized.…”

STEREOCHEMISTRY OF ADAMANTANOID [μ-SPh)6(CdCl)4]2- ANIONS

“…The syntheses of (Cat) 2 [Cd 4^-SPh) 6 Cl 4 were carried out following the procedure of [6], For the starting material, Cd(SPh)2 was prepared by an adaptation of the literature synthesis of Zn(SR) 2 …”

“…Systematic investigations on the influences of the various factors on the stereochemistry of these adamantane-like structures are scarce. The aim of the present work is to investigate the influence of the cations on the stereochemistry of the adamantane-like [Cd 4^-SPh) 6 Cl 4 ] 2 " anions. When (Me 4 N)2[Zn4^-SePh)io] was prepared in two different solvent systems, the compound crystallized in two different space groups.…”

“…Recently it has been shown that changing the terminal ligand from CI to I has little systematic effect on configurational isomerism and geometry of (Μ6 4 Ν) 2 [(μ-8Ρ1ι) 6 (ΖηΧ) 4 ] (X = CI, Br, I) [4]. The anion [Cd 4^-SPh) 6 Cl 4 ] 2 " is chosen since the syntheses and chemistry of this anion is well established [6] and the corresponding Br derivative belongs to the rare isomer IV [7], However in both compounds, the anions have the same stereochemistry [5], It appears that solvents do influence the structure if not on the stereochemistry in both compounds.…”

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The crystal and molecular structures of compounds (Cat>2[Cd 4^-SPh) 6 Cl 4 ] (Cat = Et^N^.l; Pr^N 4 ". 2; Bu^N", 3) have been determined by single crystal X-ray (Effraction techniques to study the influence of the cations on the stereochemistry and configurational isomerism of the [Cd 4^-SPh) 6 Cl 4 ] 2 " anions.

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