Preparation, crystal structure, and spectroscopic characterization of the tetranuclear copper-thiolate cluster [Cu4(o-(SCH2)2C6H4)3]2- as its tetraphenylphosphonium(1+) salt

Abstract

Supplementary Material Available: Listings of all the calculated atomic coordinates, anisotropic thermal parameters, isotropic thermal parameters for hydrogen atoms, remaining bond lengths and bond angles, and |F0| and |FC| values (40 pages). Ordering information is given on any current masthead page.

Synthesis and X‐ray Characterization of Mono‐ and Polynuclear Thiolatocopper(I) Complexes: The Effect of Steric Bulk on Coordination Number and Nuclearity

“…The structure features an adamantane-like tetrahedron of metal atoms enveloped by a disordered octahedron of six µ 2 -thiolato ligands. [22][23][24][27][28][29][30][37][38][39] Each of the six ligand units in the tetranuclear copper(I) cluster bridges the edges of the tetrahedral array of copper atoms, and each copper center is three-coordinate with high planarity of the trigonal geometry (sum of the angles around the copper center of 359.6-359.9°), with a total of two Et 4 N + counterions. The high T d symmetry of the core is reduced by the substituted aromatic ligands and their position, where the aromatic rings on two of the bound thiolato ligands for three of the four copper atoms [Cu(1), Cu(2), and Cu(3); Figure 6] face in opposite directions rather than giving the propeller-type geometry observed for Cu (4).…”

Flexible CuI–Thiolate Clusters with Relevance to Metallothioneins

“…Each sulfur atom of the phenylthiolate ligand within the cluster adopts an approximate tetrahedral geometry that coordinates three trigonally coordinated copper atoms (triply bridging thiolate ligand). The Cu-S bond lengths [mean 2.2465(17) Å for 1 and mean 2.2502(18) Å for 2] [35] are dependent on the coordination number of the copper atom and distinct ranges can be distinguished: 2.14-2.17 Å for two coordinate [29,36] copper atoms, 2.22-2.23 Å for three coordinate [18,[23][24][25][26]37] copper atoms and 2.33-2.48 Å for four coordinate [38][39][40] copper atoms, and the Cu···Cu separations range from 2.8622(12) to 4.0699(13) Å for 1 and from 2.8242(13) to 4.0557(13) Å for 2. Bond lengths and angles are listed in Table 1.…”

“…Among the common Cu n clusters (n = 4, [12] 6, [8,9] 7 [13] and 8 [10,11] ) known to be present in Cu-MT, the varied ligation number of the thiolate ion (CysS m , m = 4 to 11) contributes to the diverse stoichiometry that one can anticipate in Cu-MT clusters. Accordingly, many examples of monodentate thiolatocopper(I) clusters have been reported so far by X-ray crystallography [14][15][16] [CuS 2 , [17] CuS 3 , [18,19] Cu 2 S 2 , [20] Cu 3 S 3 , [21] Cu 4 S 4 , [22] Cu 4 S 6 , [18,[23][24][25][26] Cu 5 S 6 , [27,28] Cu 5 S 7 , [29] Cu 6 S 4 (in this work) Cu 7 S 8 , [30] Cu 8 S 8 [31] and Cu 12 S 12 [32] ]. 6 ] (4).…”

Nanoparticles: Uses and Relationships to Molecular Cluster Compounds

“…7a,b). In a set of examples from the cluster literature, 1,2-dithiolates, 1,3-dithiolates, and 1,4-dithiolates [38,39] all serve as sulfur centers (edges) in adamantanoid Cu 4 (S±R±S) 3…”